KR100255068B1 - Flame retardant for styrene resin and composition - Google Patents

Abstract

Low volatility flame retardants for styrene resins consisting of aromatic phosphates represented by formula (I):

[Formula I]

Wherein a, b, and c independently represent an integer of 1 to 3; R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a halogen-free alkyl group having 1 to 30 carbon atoms and isopropyl The total number of carbon atoms in the substituents represented by R ₁ , R ₂ , and R ₃ is on average 12 to 25 per molecule of aromatic phosphate, provided that the substituents of the plurality of said aromatic phosphates, flame retardants having different substituents The total number of carbon atoms in R ₁ , R ₂ , and R ₃ is expressed as the total number average of flame retardants, which is the sum of the product of the mass portion of each said aromatic phosphate and the total number of carbon atoms of the substituents in said aromatic phosphate, respectively)) .

Description

[Name of invention]

Low volatility flame retardant for styrene resin

[Technical Field]

The present invention relates to a low volatility flame retardant for styrene resins. More specifically, the present invention relates to a low volatility flame retardant for styrene resins, a resin composition comprising the flame retardant, in which no molding deposit is produced even after the molding continues to extend.

[Background]

Due to its excellent formability as well as its excellent impact resistance, styrene resins have been widely applied in many fields such as automotive, home appliances and office automation (OA) equipment. However, styrene resins have been limited in use due to their flammability.

A known method for egg salting styrene resins is to incorporate halogen, phosphorus or inorganic flame retardants into the styrene resin. The method can achieve to some degree egg resistance. However, halogen flame retardants adversely harm the environment. The use of phosphorus or inorganic flame retardants is not satisfactory in the results of impact strength, melt flow and heat resistance. In addition, non-volatile organophosphorus compounds can cause molding stains that reduce productivity, such as so-called molding deposits during molding. Molding stains can be transferred to the molded product and cause its stress cracking. Thus, industrial use is limited.

Phenolic resins and certain monomeric alkyl-substituted phosphates as an approach to improving volatility (JP-A 1-95143 (the term “JP-A” as used herein means “Unexamined Japanese Patent Application), The resin composition for laminated bodies which consists of JP-A-1-242633 and JP-A 1-193328) is improved. The flame retardant set forth in this document is applied to thermosetting resins. Therefore, the flame retardant is not a flame retardant for styrene resin of the present invention.

Antistatic agents consisting of phosphates such as sulfonate and dinonylphenyl phenylphosphate (JP-A No. 3-64368) and triaryl phosphates such as polyol esters and bisnonylphenyl phenylphosphate (US Pat. No. 4,780,229) are disclosed. . However, the compounds disclosed in this document are not flame retardants and are essentially different from the present invention.

This is a resin composition consisting of polycarbonate, ABS resin, halogenated phosphate and polytetrafluoroethylene (WO 9106598), polycarbonate, AAS resin, phosphate and polytetrafluoroethylene (EP 534297) resin composition, polycarbonate, Resin composition consisting of ABS resin, phosphate and polytetrafluoroethylene (DE 4309142), polycarbonate, resin composition consisting of metal salt of ABS resin, aromatic phosphate and aromatic sulfuric acid (JP-A-6-299060), polycarbonate, Polyester resins are known, consisting of polycarbonates, ABS resins, phosphates and polytetrafluoroethylene (EP 482451), and polycarbonates, ABS resins, phosphates and polycarbonate-siloxane block copolymers (DE 4016417). The phosphate to be incorporated in the aforementioned polycarbonate resin composition consists of the absence of phosphates with specific substituents and therefore a poor balance between non-volatile and flame retardants.

Also, a flame retardant consisting of a phenyl group, an isopropylphenyl group and a C _4-12 alkyl-substituted phenyl group (JP-A-2-792 corresponding to EP 324716), polyphenylene ether, styrene resin and tris (isopropylphenyl) Flame retardant resins consisting of phosphate (JP-A-1-48844) and functional fluid compositions consisting of polystyrene, t-butylphenyl phenylphosphate and polyol esters (USP 4645615) are disclosed. The number average of the total number of carbon atoms in the substituents in the phosphate of this document is less than 12 based on the definitions in the present invention described below. Thus, the compound is insufficient in nonvolatile.

As used herein, the expression “C _Xy alkyl” and the like means “alkyl having x to y carbon atoms” and the like.

Also disclosed are flame retardant resin compositions consisting of phosphates, wherein substituents R ₁ , R ₂ and R ₃ in formula (I) of the present invention to be described below are tris (4-phenylphenyl) phosphate and tris (benzylphenyl), respectively. ) Aromatic hydrocarbons such as phosphate (DE 4016417, EP 534297, EP 534297).

Flame retardant resin compositions consisting of polyphenylene ethers, styrene resins, metal salts of phosphoric acid and phosphates such as tris (nonylphenyl) phosphate (JP-A-63-305161), polyphenylene ethers and Essential compounds include polyphenylene ether resin compositions consisting of high molecular weight polyethylene, and optionally phosphates such as tris (nonylphenyl) phosphate (EP 550204), and aromatic polycarbonates, ABS resins, AS resins, tris (nonylphenyl) phosphates A flame retardant resin composition consisting of phosphate, aromatic sulfonates and fibrous reinforcing agents (JP-A No. 6-299060) is disclosed. The resin compositions disclosed above in this document consist of phosphates such as tris (nonylphenyl) phosphate and therefore exhibit low flame retardancy. The resin composition appears to significantly reduce the heat resistance when incorporating the above-described large amount of phosphate to improve its flame retardancy. In addition, the document states that the mixing of tris (nonylphenyl) phosphate, bis (nonylphenyl) phenylphosphate and nonylphenyl diphenylphosphate provides a marked improvement in the balance of flame retardancy, dissolution flowability, heat resistance, impact strength and water gloss retention. Does not start.

C _4-22 alkyl group, C _12-22 alkenyl group, phenyl group and C _7-15 alkyl phenyl group (alkyl moiety having 1 to 9 carbon atoms) as an approach for flame retardancy of styrene resin (JP-A-3-294284) A method for preparing a triester phosphate consisting of a hydrocarbon group selected from the group consisting of is disclosed. This document differs not only from the present invention with respect to the preparation process, but also discloses or suggests that certain substituent-containing monomeric aromatic phosphates provide a marked improvement in continuous formability (non-volatile) while retaining styrene resins, especially flame retardants. Do not.

A monomer phosphate composed of a plurality of isopropyl groups and a flame retardant composition composed identically are disclosed (GB 2027712 corresponding to US 4370281 and JP-B 63-61313) (the term “JP-B” as used herein refers to a “examined Japanese patent). Announcement ”).

The total number of carbon atoms in the substituents in the phosphates of this document is on the order of 6 to 47, based on the definition of the present invention. In addition, the documents do not disclose the fact that substituents having a specific total number of carbon atoms on the number average merely provide a sufficient balance between flame retardancy and non-volatility. In addition, the document does not mention the fact that the incorporation of certain substituents of the invention can provide an improvement in flame retardancy, in particular drop ductility. In addition, since the flame retardant according to the present invention is composed of a plurality of isopropyl groups as a substituent, it exhibits not only high viscosity that can be easily handled, but also very low light resistance in practical use.

Detailed description of the invention

It is an object of the present invention to provide a resin composition consisting of (low volatility) flame retardants and the flame retardants which are free from the above-mentioned problems, for example, even after continuous extended molding, without molding deposits.

The present inventors have been in-depth researching techniques for suppressing molding deposits as an indicator of non-volatility. As a result, it has been surprisingly found that the use of aromatic phosphates containing specific substituents as flame retardants dramatically improves the flame retardancy of styrene resins while suppressing molding deposits. Thus, the present invention solved the problem.

The present invention in its main aspect is formula (I):

[Formula I]

(Wherein a, b, and c each independently represent an integer of 1 to 3; R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a halogen-free alkyl group having 1 to 30 carbon atoms, and iso The total number of carbon atoms in the substituents represented by R ₁ , R ₂ , and R ₃ is not a propyl group, but averages 12 to 25 in one molecule of aromatic phosphate, provided that the substituents of a plurality of aromatic phosphates and flame retardants having different substituents The total number of carbon atoms in R ₁ , R ₂ , and R ₃ is expressed as the total number average of flame retardants, which is the sum of the product of the weight fraction of each aromatic phosphate and the total number of carbon atoms of the substituents in each aromatic phosphate) A low volatility flame retardant for styrene resins comprising aromatic phosphates.

The invention also relates to a resin composition consisting of 100 parts by weight of styrene resin and 1 to 50 parts by weight of the flame retardant of the invention.

[Brief Description of Drawings]

1 is measured by the flame retardancy (time after burning: second) and thermogravimetric analysis (TGA method) of the molded product of the resin composition described in Table 2 and stored at 250 ° C. for 5 minutes, followed by the residual amount and number average phase of the monomer aromatic phosphate. The relationship of the total number of carbon atoms in the substituent of the monomeric aromatic phosphate to is described;

2 illustrates the results of thermogravimetric analysis (TGA method) of unsubstituted monomeric aromatic phosphate (TPP), alkyl group-substituted monomeric aromatic phosphate (BNPP) and oligomeric aromatic phosphate (fr-1);

3 shows the ratio of the resin composition consisting of alkyl group-substituted monomeric aromatic phosphates (BNPP) and oligomeric aromatic phosphates (fr-1) (Example 18 and Comparative Example 25 in Table 4) and the base resin measured by a cone calorimeter. It is about;

4 relates to the content of oligomeric aromatic phosphates (fr-1) in resin compositions (Table 4) consisting of alkyl group-substituted monomeric aromatic phosphates (BNPP, TNPP) and oligomeric aromatic phosphates (fr-1) and their flame retardancy;

FIG. 5 relates to the addition of PPE based on 100 parts by weight of rubber-modified styrene resin with MFR, non-cat softening temperature and flame retardancy as described in Table 10;

FIG. 6 relates to the composition ratio of HIPS to Falling Impact Strength (kgcm (2mm thickness)), Curved Modulus (kg / cm ² ) and Glossy Small Size Particle Rubber (Examples 61-65) as Large Size Particle Rubber. ;

FIG. 7 relates to the composition ratio of GPPS with different molecular weights in rubber-modified styrene resins (Examples 66-68) having a fall impact strength (kgcm (2 mm thick)) and MFR (g / 10 min);

8 is a monomer aromatic consisting of NDPP, BNPP and TNPP as described in Tables 13-1 and 13-2 on MFR, non-cat softening temperature, number average with residual amount and water-resistant gloss retention after 5 minutes storage at 250 ° C. It relates to the total number of carbon atoms in the substituent of the monomeric aromatic phosphate obtained by changing the percent composition of phosphate;

9 relates to the relationship between the total content of residual styrene monomers and dimerization and trimerization products of styrene and their flame retardancy (time after flame: seconds) in the resin compositions described in Table 19;

10 is a typical example of a double screw extruder, wherein the shaded portion represents the kneading zone;

11 illustrates a supply method for various components of the resin composition; And

FIG. 12 illustrates the relationship between the kneading parameters and the fall impact strengths of the examples and comparative examples described in Table 26 as indicators of kneading, where the ordinate represents the fall impact strength (kgcm) and the abscissa is the kneading property. Indicates parameters (extrusion factor / rotation speed).

[Best way to apply invention]

The low volatility flame retardant (component A) for styrene resin of this invention consists of monomeric aromatic phosphates which have a specific substituent.

It is important that the aforementioned monomeric aromatic phosphates are in monomeric form rather than oligomeric products. Since monomeric aromatic phosphates are in the form of monomers, they can be sufficiently evaporated during the initial combustion stage. In particular, when the flame retardant styrene resin is added dropwise, since the monomer aromatic phosphate is a monomer, the plasticity of the styrene resin is accelerated to improve its dropping property during combustion.

Substituents R ₁ , R ₂ and R ₃ in monomeric aromatic phosphates each represent a hydrogen atom or a C _1-30 alkyl group. It is important that the total number of carbon atoms in the substituents R ₁ , R ₂ and R ₃ is 12 to 25 as the total compound. If the number average total number of carbon atoms is 12 or less, excellent flame retardancy is obtained, but becomes high volatility. If the number average total number of carbon atoms exceeds 25, the flame retardancy is reduced.

Aromatic phosphates that meet the above requirements show a mass loss of 0 to 10% by weight at 300 ° C in a heating test (temperature rise rate: 40 ° C / min) in nitrogen and 30 to 100% by weight at 400 ° C, preferably 50 to A mass loss of 100% by weight is shown. That is, since the mass loss at 300 ° C. does not exceed 10% by weight, no molding deposit occurs during molding of the styrene resin. Therefore, the present invention also exhibits a mass loss of 0 to 10% by weight at 300 ° C and a mass loss of 50 to 100% by weight at 400 ° C with a temperature rise rate of 40 ° C / min when heated in nitrogen. A volatile aromatic phosphate-flame retardant. The aromatic phosphate suddenly evaporates at a temperature of 400 ° C. during the initial combustion phase, so that the resulting gas phase effect develops flame retardancy. In addition, incorporation of specific substituents has improved compatibility with the styrene resin, so that the dropping properties of the resin are significantly accelerated. Thus, the present invention solved the problem.

The monomeric aromatic phosphate containing the low volatile flame retardant (component A) for styrene resin of the present invention is represented by the formula (I):

[Formula I]

(Wherein a, b, and c each independently represent an integer of 1 to 3; R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a halogen-free alkyl group having 1 to 30 carbon atoms, The total number of carbon atoms in the substituents represented by R ₁ , R ₂ , and R ₃ is not isopropyl group and averages 12 to 25 in one molecule of aromatic phosphate, provided that a plurality of aromatic phosphates and flame retardants having different substituents The total number of carbon atoms in substituents R ₁ , R ₂ , and R ₃ is expressed as a number average throughout the flame retardant, which is the sum of the product of the weight portion of each aromatic phosphate and the total number of carbon atoms in the substituents in each aromatic phosphate))) It is expressed as

In the monomeric aromatic phosphates of the present invention, the total number of carbon atoms in the substituents R ₁ , R ₂ and R ₃ is preferably on average 14 to 22, more preferably 16 to 20 and most preferably 17 to 19.

Specific examples of the substituent include nonyl group, butyl group such as t-butyl, t-amyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and octadodecyl group. One or a plurality of substituents may be substituted with respect to the aromatic ring on either ortho, meta or para position, preferably on the para position. Most preferably, the total number of carbon atoms in the alkyl group substituted on one monomer phosphate is 12 to 25. Monomer phosphates having a plurality of aromatic rings substituted by one alkyl group have better heat resistance and water resistance than monomer phosphates having only one aromatic ring substituted by only one long chain alkyl group. For example, although the total number of carbon atoms in the alkyl group as a substituent is 18, bis (nonylphenyl) phenylphosphate is higher in heat resistance and more preferred than octadecylphenyl diphenylphosphate.

Particularly preferred flame retardants of the invention are monomeric phosphates, wherein at least one of R ₁ , R ₂ and R ₃ is a nonyl group. Among the most preferred flame retardants of the present invention are bis (nonylphenyl) phenylphosphates, wherein R ₁ and R ₂ are each nonyl groups and R ₃ is a hydrogen atom. These monomer phosphates can exhibit particularly great effects when incorporated into the flame retardant in an amount of at least 50% by weight. In addition, the monomeric aromatic phosphates exhibit excellent flame dropping properties. Monomer phosphate is extremely good as a V-2 flame retardant according to standard flame retardancy on the basis of UL-94. This fact was not previously known.

In terms of non-volatility, the total number of carbon atoms in the substituents needs to satisfy the requirements of the present invention. If the content of the compound in which the total number of carbon atoms in the substituent falls below 12 is 20% by weight or less, it can become higher nonvolatile.

In terms of thermal stability of the flame retardant, in particular heat dissipation, the acid value as defined in JIS-K6751 as an index of remaining acidic substance is preferably 1 mgKOH / g or less, more preferably 0.5 mgKOH / g or less, and / Or the alkylphenol content is preferably 1% by weight or less, more preferably 0.5% by weight or less. It is also preferred that the total content of aluminum, magnesium, sodium and antimony is 1,000 ppm by weight or less.

It is also desirable to incorporate phenolic antioxidants suppressed in flame retardants in amounts of 1 to 1,000 ppm by weight, since thermal stability can be dramatically improved.

In terms of light resistance, the substituents R ₁ , R ₂ , and R ₃ are rather branched alkyl groups, in particular linear alkyl groups or alkyl groups with only one branch, rather than aryl groups. Even when branched at one position, alkyl groups having up to 5 carbon atoms show poor light resistance. Monomer phosphates with isopropyl groups exhibit extremely poor light resistance.

In addition, the number of substituents on one aromatic ring in aromatic phosphate is preferably one. Monomer phosphates having a plurality of substituents in one aromatic ring exhibit high viscosity. The viscosity occurs as a plurality of substituents on one aromatic ring. When the viscosity of the monomer phosphate occurs, the compound not only suffers from manipulation problems, but also becomes difficult to purify, which leads to deterioration of light resistance and thermal decolorization since the aforementioned impurities are left to stand.

Most preferred mixtures of monomeric aromatic phosphates of the present invention are nonylphenyl diphenylphosphate (NPDP represented by Formula I (wherein R ₁ and R ₂ each represent a hydrogen atom and R ₃ represents a nonyl group)), bis (nonylphenyl Phenylphosphate (BNPP represented by formula I (wherein R ₁ represents a hydrogen atom and R ₂ and R ₃ each represent a nonyl group)) and tris (nonylphenyl) phosphate (wherein TNPP represented by formula (I) ₁ , R ₂ and R ₃ each represent a nonyl group)), and the total number of substituents R ₁ , R ₂ and R ₃ is 12 to 25, preferably 14 to 22, and more preferably 16 to 22, on a number average. 20, most preferably 17 to 19. In order to satisfy the aforementioned number average total number of carbon atoms, the NPDP content is generally 1 to 80% by weight, preferably 1 to 50% by weight, more preferably 1 to 30% by weight, most preferably 1 to 10% by weight. %, BNPP content is generally 1 to 98% by weight, preferably 20 to 90% by weight, more preferably 30 to 80% by weight, most preferably 40 to 80% by weight, and TNPP content is generally 1 to 98% by weight, preferably 1 to 70% by weight, more preferably 5 to 60% by weight, most preferably 5 to 50% by weight. The flame retardant having such a mixture is particularly excellent in balance of flame retardancy, melt flowability, heat resistance, impact strength, water gloss retention, and surface hardening of the obtained molded product. Mixing of monomeric aromatic phosphates with different numbers of substituted nonyl groups in a premeasured amount has a particular effect. NPDP has a high plasticizing effect. NPDP not only acts as a melt flow improver but also has a great impact on improving flame retardancy. TNPP exhibits extremely good water-resistant gloss retention as well as a great effect of providing non-volatile and heat resistance. BNPP is a good balance of the above characteristics. The combination of three components in a pre-measured amount can provide well-balanced properties that cannot be obtained using one of the three components. In particular, the improvement of the water gloss retention and the surface hardening of the molded product cannot be predicted from the common knowledge.

The preparation of the monomeric aromatic phosphates of the present invention can be accomplished, for example, by the known methods disclosed in JP-A 1-95149 and JP-A 3-294284. Examples of known methods include the process consisting of reacting alkylphenols with phosphorus oxychloride in the presence of aluminum chloride anhydride as a catalyst under heating, and converting the triester phosphite with oxygen to convert to the corresponding aromatic phosphate. Include.

When the low volatile flame retardant for styrene resin of the present invention is added to the styrene resin to prepare a resin composition, the flame retardant is 1 to 50 parts by weight, more preferably 1 to 20 parts by weight, most preferably 3 per 100 parts by weight of the styrene resin. It is preferable to incorporate in the resin composition in an amount of from 8 parts by weight.

Styrene resins (component B) capable of incorporating low volatility flame retardants for styrene resins of the present invention are rubber-modified styrene resins and / or unmodified styrene resins and may be miscible with component A or may be uniformly dispersed. One is not particularly limited. Preferably, rubber-modified styrene resins or mixtures of unmodified styrene resins are used. The rubber-modified styrene resin is a polymer consisting of a matrix of vinyl aromatic polymers having a particulate rubbery polymer dispersed therein and optionally together therein in the presence of bulk polymerization, bulk suspension polymerization, solution polymerization or aromatic vinyl monomers and rubbery polymers. It can be obtained by emulsion polymerization of a monomer mixture consisting of copolymerizable vinyl monomers.

Examples of the resin include impact resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), and AES resin (acrylonitrile-ethylenepropylene rubber- Styrene copolymers).

The aforementioned rubbery polymer should exhibit a glass transition temperature (Tg) of -30 ° C or below. If the glass transition temperature exceeds -30 ° C, the resulting composition exhibits reduced impact resistance.

Examples of rubbery polymers include diene rubbers such as (polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene)), saturated rubbers obtained by hydrogenating the aforementioned diene rubber, isoprene rubber, chloroprene rubber, ( Acrylic rubbers such as poly (butyl acrylate)), and ethylene-propylene-diene monomer terpolymers (EPDM). Particularly preferred among these rubbery polymers is diene rubber.

Examples of aromatic vinyl monomers as essential components to be incorporated in the graft polymerizable monomers to be polymerized in the presence of the above-mentioned rubbery polymers include styrene, α-methylstyrene, and paramethylstyrene. Most preferred of these aromatic vinyl monomers are styrene. Styrene can be copolymerized with the other aromatic vinyl monomers described above as main components.

One or more copolymerizable monomer components as constituents of the rubbery styrene may be incorporated into the aromatic vinyl monomer if necessary. If the oil resistance of the composition is needed for improvement, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.

If it is necessary to reduce the melt viscosity during blending, acrylates with C _1-8 alkyl groups can be used. In addition, if it is necessary to improve the heat resistance of the resin composition, monomers such as α-methylstyrene, acrylic acid, methacrylic acid, maleic anhydride and N-substituted maleimide may be copolymerized. Among them, α-methylstyrene and butyl acrylate are excellent when providing dropwise flame retardancy. The content of the vinyl monomer copolymerizable with the above-mentioned vinyl aromatic monomer in the monomer mixture is generally 0 to 40% by weight.

The content of the rubbery polymer in the rubber-modified styrene resin is preferably 5 to 80% by weight, in particular 10 to 50% by weight. The content of the graft-copolymerizable monomer mixture in the rubber-modified styrene resin is preferably 20 to 95% by weight, more preferably 50 to 90% by weight. Within this range, the resin composition exhibits an improved balance in impact resistance and robustness. In addition, the diameter of the particle rubber in the styrene polymer is preferably 0.1 to 5.0 mu m, preferably 0.2 to 3.0 mu m, most preferably 1.0 to 2.0 mu m. Within this range, the impact resistance of the rubber-modified styrene resin is improved.

The converted viscosity η SP / C of the resin portion as a measure of the molecular weight of the rubber-modified styrene resin is preferably 0.30 to 0.80 dl / g, more preferably 0.40 to 0 / 0.6 dl / g (when the matrix resin is polystyrene In a toluene solution or when the matrix resin is an unsaturated nitrile-aromatic vinyl copolymer, measured as 0.5 g / dl at a temperature of 30 ° C. in methyl ethyl ketone). As a method of satisfying the above-mentioned demand for the converted viscosity η SP / C of the rubber-modified styrene resin, one that adopts the amount of the polymerization initiator, the polymerization temperature, the amount of the chain transfer agent, and the like can be used.

In general, rubber-modified styrene resins having a converted viscosity η SP / C of 0.40 to 0.60 dl / g are excellent in melt flowability and excellent in flame retardancy, especially dropwise flame retardancy, but exhibit poor impact strength. The inventors performed a high degree of grafting of vinyl aromatic monomers on conjugated diene polymers, the most remaining unsaturated bonds being 1,4-bonds, in the presence of organic peroxides with high hydrogen absorption capacity. As a result, rubber-modified styrene resins having high impact strength and toughness having a specific particle diameter distribution have been successfully prepared in the dispersed phase of the conjugated diene polymer.

More specifically, 60 to 96% by weight of styrene and other vinyl aromatic monomers, optionally copolymerizable with styrene, 4 to 15% by weight of conjugated diene polymer or partially hydrogenated, wherein at least 95% of the remaining unsaturated bonds are 1,4-structured A polymer mother liquor consisting of a conjugated diene polymer and an organic peroxide having a hydrogen absorption capacity ε of at least 35 in an amount of 0.0002 to 0.0006 with respect to the previous vinyl aromatic amount such as styrene until the conversion rate of the vinyl aromatic monomer reaches 30%. While maintaining the plug flow type polymerization reactor, the polymerization temperature and the solution feed rate are controlled continuously so that the average polymerization rate is 10 to 15% hr until the conversion rate of the vinyl aromatic monomer reaches 30% or more. By supplying the device, the desired rubber-modified styrene resin can be produced. As used herein, the term “hydrogen absorption capacity ε” refers to the number of moles of n-pentadecan dimer produced by heating a solution of about 1 mmol / L n-pentadecane of the aforementioned organic peroxide to a temperature having a half-life of 15 minutes for 150 minutes. It means dividing by the number of moles of peroxide, and then multiply by 100 to show the quotient obtained.

The obtained rubber-modified styrene resin consists of small particles having a diameter of 0.1 to 0.4 mu m and large particles having a diameter of 1.0 to 8.0 mu m in the dispersed phase. Small particles and large particles in all particles are 10-50%, and 50-90%, respectively, in terms of area. Small sized particles are composed of cell structures at a rate of 50% or more, calculated in terms of area. The large sized particles have a structure of enclosing the outermost outer circumference and incorporating any of the maze, reel and fiber bundle arrangements therein at a rate of 50% or more calculated in terms of area.

Particle rubbers constituting the rubber-modified styrene resin are preferably small size particles having a weight-average particle diameter of 0.1 to 0.9 mu m in view of the balance of the appearance (gloss), impact strength and toughness of the obtained molded product. Rubber and large sized particle rubbers having a weight-average particle diameter of 1.0 to 3.0 μm.

When the weight-average particle diameter of the small sized particle rubber is 0.1 μm or less, the resulting molded product tends to appear to have reduced impact strength and flame retardancy.

If the weight-average particle diameter of the small sized particle rubber exceeds 0.9 mu m, the resulting molded product tends to appear to decrease in toughness and to weaken in appearance (gloss). In addition, when the weight-average particle diameter of the large sized particle rubber is 1.0 mu m or less, the resulting molded product tends to appear to decrease in impact strength and flame retardancy. When the weight-average particle diameter of the large sized particle rubber exceeds 3.0 mu m, the resultant molded products tend to appear to have reduced impact strength and toughness and weaken the appearance (gloss).

The small particle rubber described above has a capsule structure made of a block copolymer of styrene and 1,3-butadiene (particle structure with only one occlusion in one rubber particle). The large sized particle rubber described above has a multi-area structure made of a “salami” structure or, for example, polybutadiene (a particle structure having a plurality of occlusions in one rubber particle). The portion of the former in the rubber-modified styrene resin is preferably 20 to 80% by weight, and the latter portion in the rubber-modified styrene resin is preferably 20 to 80% by weight.

The aforementioned block copolymers of styrene and 1,3-butadiene preferably have a butadiene content of 15 to 35% by weight. It is structurally represented by SBSB or SBS, where S represents a styrene polymer block and B represents a polymer block composed mainly of 1,3-butadiene or butadiene.

Rubber-modified styrene resins consisting of large-size particle rubbers and small-size particle rubbers are prepared separately from rubber-modified styrene resins containing small-size particle rubbers and rubber-modified styrene resins containing large-size particle rubbers. The rubber-modified styrene resin may be blended in an extruder, or may be prepared by mixing two rubber-modified styrene resins in a polymerization reactor. More specifically, the block polymerization method is preferably a particle of a particle rubber when a homogeneous polymerization mother liquid consisting of a rubbery polymer, a monomer mixture and a polymerization solvent is subjected to continuous polymerization and devolatilization and produced by a bulk polymerization method. When the diameter is adjusted to the number of revolutions to agitation, it is used to consist of feeding into the stirred continuous multistage bulk polymerization reactor. The larger the rotation speed, the smaller the particle diameter. The smaller the rotation speed, the larger the particle diameter.

The low volatile flame retardant for styrene resin of the present invention can be incorporated into a resin composition composed of a styrene resin blended with another thermoplastic resin. For example, polyphenylene ether resin, polyamide resin, polyester resin, polyphenylene sulfide resin, polycarbonate resin or polymethacrylate resin can be used alone, and two or more of the above resins can be used in combination. Can be. Preferred examples of the thermoplastic resin that can be mixed with the styrene resin include polyphenylene ether thermoplastic resins and polycarbonate thermoplastic resins. The content of other thermoplastic resins in the mixture of styrene resins and other thermoplastic resins is preferably 0 to 90% by weight, more preferably 0 to 70% by weight, most preferably 3 to 40% by weight.

Polyphenylene ethers (component C) which can be incorporated into styrene resins are represented by the formula (II):

[Formula II]

A homopolymer and / or a repeating unit represented by (wherein R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of a hydrogen atom, a hydrocarbon group and a substituted hydrocarbon group and may be the same or different) Copolymer.

Particularly preferred examples of polyphenylene ethers include poly (2,6-dimethyl-1,4-phenylene ether), and copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol.

Particularly preferred among the polyphenylene ethers is poly (2,6-dimethyl-1,4-phenylene ether). The method for producing the polyphenylene ether is not particularly limited. For example, the polyphenylene ether can be readily prepared by performing oxidative polymerization in the presence of a complex of amine and cuprous oxide as described in US Pat. No. 3,306,874. These methods, US Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, JP-B 52-17880, and JP-A 50-51197 can also be used to readily prepare such polyphenylene ethers. have.

The converted viscosity η SP / C of the aforementioned polyphenylene ether to be used in the present invention is preferably 0.20 to 0.70 dl / g, more preferably 0.30 to 0.60 dl / in view of dissolution flowability and flame retardancy, particularly dropwise flame retardancy. g (30 ° C., measured as 0.5 dl / g in chloroform solution). Examples of methods for meeting the aforementioned needs for the reduced viscosity η SP / C of polyphenylene ethers include controlling the amount of catalyst to be used in the preparation of polyphenylene ethers.

The amount of polyphenylene ether to be used is preferably 1 to 40 parts by weight, more preferably 1 to 10 parts by weight, most preferably 3 to 8 parts by weight per 100 parts by weight of the styrene resin to be used.

As a thermoplastic resin that can be incorporated into the styrene resin, a phosgene method is used in which an aromatic polycarbonate is bubbled into an aromatic divalent phenol compound in the presence of a caustic alkali and a solvent, or an aromatic divalent phenol compound and diethyl carbonate can be subjected to ester interchange in the presence of a catalyst. It can be obtained by the ester interchange method performed. The preferred viscosity-average molecular weight of the aromatic homopolycarbonate or high polycarbonate obtained is 10,000 to 100,000.

Examples of the dihydric phenol compound described above include 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxy Phenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, 2,2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxy-3,5- Diphenyl) butane, 2,2'-bis (4-hydroxy-3,5-dipropylphenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, and 1-phenyl-1, 1'-bis (4-hydroxyphenyl) ethane. Particularly preferred among the dihydric phenol compounds is 2,2'-bis (4-hydroxyphenyl) propane (bisphenol A). The divalent phenolic compound of this invention can be used individually or in mixture.

The amount of polycarbonate used is preferably 1 to 40 parts by weight, more preferably 1 to 10 parts by weight, most preferably 3 to 7 parts by weight, per 100 parts by weight of the styrene resin used.

According to the kind of resin composition, the low volatile flame retardant for styrene resins of this invention is used together with polyorganopolysiloxane (component D), and the orientation of a styrene resin is relieved. If high shear forces are used during molding, the resulting molded product is oriented therein and dropping during combustion is suppressed. Therefore, the specific kinematic viscosity relaxes the orientation of the resin composition, resulting in unstable molecular chains. As a result, the dropping property of the molded product of the resin composition can be improved. The kinematic viscosity (25 ° C.) of the aforementioned polyorganosiloxane is preferably 30 to 20,000 CS, more preferably 40 to 1,000 CS, and most preferably 50 to 100 CS. When the kinematic viscosity of the above-mentioned polyorganosiloxane falls below 30 CS, the polyorganosiloxane exhibits high volatility and thus shows a molding delay. When the kinematic viscosity of the polyorganosiloxane described above exceeds 20,000 CS, the effect as a result of the relaxation of the orientation of the styrene resin is reduced.

As polyorganosiloxane as component D, polydimethylsiloxanes such as so-called silicone oils are preferably used.

The amount of polyorganosiloxane used is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, most preferably 0.3 to 3 parts by weight per 100 parts by weight of the styrene resin used.

The low volatile flame retardant for styrene resin of the present invention can be used as the flame retardant (component E) other than the flame retardant (component A) of the present invention such as organophosphorus compound, red, inorganic phosphorus salt, inorganic flame retardant, etc. if necessary according to the resin composition. .

The amount of component E used is preferably 1 to 40 parts by weight, more preferably 1 to 20 parts by weight, most preferably 5 to 10 parts by weight per 100 parts by weight of the styrene resin used.

Examples of organophosphorus compounds as component E include phosphines, phosphine oxides, biphosphines, phosphonium salts, phosphonates, phosphates, and phosphites. Specific examples of the organophosphorus compound include methyl neopentyl phosphite, pentaerythritol diethyl diphosphate, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypodiphosphate, di Neopentyl hypophosphite, phenylpyrrolecatecholphosphate, ethylpyrocatechol phosphate, and diprocatechol hypodiphosphate.

Oligomeric aromatic phosphates, such as tetraphenyl bisphenol A polyphosphate, can be blended into the resin composition to such an extent that its flame retardancy does not affect.

Examples of droplets to be used as component E include conventional droplets. Other examples of droplets include droplets applied as a film of a metal hydroxide selected from the group consisting of aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide; Redis applied as a film and a thermoplastic resin of a metal hydroxide selected from the group consisting of aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide; A film of metal hydroxide selected from the group consisting of aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide and a product applied continuously as a film of thermoplastic resin on a film of metal hydroxide do.

Representative examples of inorganic phosphates that can be used as component E include ammonium polyphosphate.

Examples of inorganic flame retardants that can be used as component E are aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide and tin hydroxide Hydrates of inorganic metal compounds such as hydrates of zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, and barium carbonate. The said inorganic flame retardant can be used individually or in mixture. Particularly preferred among the inorganic flame retardants is selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate and hydrocalcite, which has excellent flame retardant effect and economic advantages.

According to the type of resin composition, the low volatile flame retardant for styrene resin of the present invention can be used as triazine skeleton-containing compound, novolak resin, metal-containing silicone oil, silica, aramid fiber, fluorine resin and polyacrylonitrile fiber. It can be used with one or more auxiliary flame retardants (component F) selected from the group consisting of.

The amount of component F to be used is preferably 0.001 to 40 parts by weight, more preferably 1 to 20 parts by weight, most preferably 5 to 10 parts by weight per 100 parts by weight of the styrene resin used.

Triazine skeleton-containing compounds that can be used as component F are components for improving flame retardancy for phosphorus flame retardants. Specific examples of triazine skeleton-containing compounds include melamine, mellam, melem, melon (the product of three molecular deammonialation of three melem molecules at temperatures above 600 ° C.), malamine cyanurate, melamine phosphate, succinogu Anamine, adipoguanamine, methylglutaloguanamine, melamine resin and BT resin. Particularly preferred among the triazine skeleton-containing compounds is melamine cyanurate in terms of non-volatility. The structural formulas of melam, melem, melon, melamine cyanurate, melamine phosphate, succinoguanamine, melamine resin and BT resin are shown below.

[Melam]

[Melem]

[Melamine Cyanurate]

[Melamine Phosphate]

[Succinoguanamin]

[Melamine resin]

[BT resin]

Novolak resin as component F is an auxiliary flame retardant. It also serves as a dissolution flow and heat resistant modifier when used in combination with hydroxyl group-containing aromatic phosphates. The resin is a thermoplastic resin obtained by condensation of phenols and aldehydes in the presence of acid catalysts such as sulfuric acid and hydrochloric acid. The preparation method thereof is disclosed in, for example, "polymer experiment 5 (polycondensation and addition polymerization)", pp. 437-455, Kyoritsu Shuppan.

An example of the manufacturing method of a novolak resin is shown below.

Examples of the aforementioned phenols include phenol, o-cresol, m-cresol, p-cresol, 2,5-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethyl Phenol, pt-butylphenol, pn-octylphenol, p-stearylphenol, p-phenylphenol, p- (2-phenylethyl) phenol, o-isopropylphenol, o-isopropylphenol, m-isopropylphenol , p-methoxyphenol, p-phenoxyphenol, pyrocatechol, resorcinol, hydroquinone, salicyaldehyde, salicylic acid, p-hydroxybenzoic acid, methyl p-hydroxybenzoate, p-cyanophenol, o Cyanophenol, p-hydroxybenzenesulfonic acid, p-cyanophenol, o-cyanophenol, p-hydroxybenzenesulfonic acid, p-hydroxybenzenesulfonamide, cyclohexyl, p-hydroxybenzenesulfonate, 4-hydroxyphenylphenylphosphinic acid, methyl 4-hydroxyphenylphenylphosphinate, 4-hydroxyphenylphosphonic acid, ethyl 4-hydroxyphenylphosphonate, and diphenyl 4-hydroxyphenylphosphonate inclusive All.

Examples of the above-described aldehydes include formaldehyde, acetaldehyde, n-propanal, n-butanal, isopropanal, isobutylaldehyde, 3-methyl-n-butanal, benzaldehyde, p-tolylaldehyde, and 2-phenyl Acetaldehyde.

Metal-containing compounds that can be used as component F are metal oxides and / or metal powders. Examples of metal oxides are aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdium oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper Oxides, tungsten oxides, and the like alone or in combination of two or more thereof. Examples of metal powders are those which synthesize (alloy) aluminum, iron, titanium, manganese, zinc, molybdium, cobalt, bismuth, chromium, nickel, copper, tungsten, tin, antimony, alone or two of them. It includes.

Silicone resins that can be used as component F are silicone resins having a three-dimensional network consisting of SiO ₂ , RSiO _3/2 , R ₂ SiO and R ₃ SiO _1/2 as structural units, wherein R is methyl, ethyl and propyl And an aromatic group such as phenyl and benzyl or a substituent consisting of the above alkyl or a vinyl group incorporated therein. In particular, vinyl group-containing silicone resins are preferable. The silicone resin can be obtained by cohydrolysis of the organohalosilane corresponding to the above structural unit.

Vinyl group-containing silicone oils that can be used as component F include:

Wherein, R represents one or more kinds of substituents selected from the group consisting of a C _1-8 alkyl group, a C _6-13 aryl group and a vinyl-containing group represented by the following formula: Siloxane. Particularly preferred substituents among these are those containing a vinyl group in its molecule.

The kinematic viscosity of the vinyl group-containing silicone oil described above is preferably 600 to 1,000,000 CP (25 ° C.), more preferably 90,000 to 150,000 CP (25 ° C.).

The silica which can be used as component F is a hydrocarbon compound-coated silica obtained by treating an amorphous silicon dioxide, preferably the surface of silica with a silane coupling agent made of a hydrocarbon compound, more preferably a vinyl group-containing hydrocarbon compound- Coated silica.

Examples of the aforementioned silane coupling agents include p-styryl trimethoxysilane, vinyl trichlorosilane, vinyl tris (β-methoxyethoxy) silane, vinyl triethoxysilane, vinyl trimethoxysilane and γ-methacrylic. Vinyl group-containing silanes such as oxypropyl trimethoxysilane; epoxysilanes such as β- (3,4-ethoxycyclohexyl) ethyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, and γ-glycidoxypropyl triethoxysilane; And N-β (aminoethyl) γ-aminopropyl trimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyl triethoxysilane and N-phenyl-γ-aminopropyl Aminosilanes such as trimethoxysilane. Particularly preferred among these silane coupling agents is a silane coupling agent having a structural close to the thermoplastic resin. For example, p-styryl trimethoxysilane is preferred for styrene resins.

Treatment of the surface of silica with a silane coupling agent can be roughly divided into two groups, for example, a wet method and a dry method. The wet process consists of treating silica in a silane coupling agent solution and then drying. The dry process consists of slowly adding dropwise addition of the silane coupling agent solution to the material with stirring, followed by filling and then heat-treating the silica in a fast-stirrable apparatus such as a Henschel mixer.

Aramid fibers that can be used as component F preferably have an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 10 mm. It can be prepared by dissolving isophthalamide or polyparaphenylene terephthalamide in an amide polar solvent or sulfuric acid and then solution-spinning the material by wet or dry methods.

Fluorine resin which can be used as component F is resin which consists of fluorine atoms mixed therein.

Specific examples are the above fluororesins such as polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoro propylene polymers. The fluorine resin may also be used in admixture with monomers copolymerizable with the aforementioned fluorine-containing monomers.

The polyacrylonitrile fibers that can be used as component F preferably have an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 10 mm. The polyacrylonitrile fiber was dissolved in a solvent such as dimethylformamide, and then dissolved in the solvent in a solvent such as dry spinning or nitric acid, followed by dry-spinning the material in a 400 ° C. air stream, followed by water It can be produced by a wet spinning method consisting in wet-spinning the material.

The low volatile flame retardant for styrene resin of the present invention is required according to the type of copolymer resin, aliphatic hydrocarbon, higher aliphatic, higher aliphatic ester, higher aliphatic amide, higher aliphatic alcohol and resin composition prepared from aromatic vinyl units and acrylic ester units. It can be used in combination with one or more dissolution flow improvers (component G) selected from the group consisting of metallurgical expenditure.

The amount of component G to be used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, most preferably 1 to 5 parts by weight per 100 parts by weight of the rubber-modified styrene resin used.

Examples of aromatic vinyl units constituting the copolymer resin as component G include α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, and 2,4,5-tribromostyrene. Most preferred of these aromatic vinyl units are styrene. Alternatively, styrene as the main component and other aromatic vinyl monomers described above can be copolymerized. The aforementioned acrylic ester units include acrylic esters made with C _1-8 alkyl groups such as methyl acrylate and butyl acrylate. The content of acrylic ester units in the copolymer resin is preferably 3 to 40% by weight, more preferably 5 to 20% by weight. The solution viscosity as an indicator of the molecular weight of the aforementioned copolymers is preferably 2 to 10 cP (centipoise) (measured as a 10 wt% MEK solution at 25 ° C.). When the solution viscosity of the copolymer resin falls below 2 cP, the resulting impact strength is reduced. When the solution viscosity of the copolymer resin exceeds 10 cP, the effect of improving the dissolution fluidity is consequently reduced.

Examples of aliphatic hydrocarbon functional acids as component G include liquid paraffins, natural paraffins, microwaxes, polyolefin waxes, synthetic waxes, partial oxidation products thereof, fluorides thereof, and chlorides thereof.

Examples of higher aliphatic as component G include saturated aliphatic compounds such as capric acid, hexadecanoic acid, partic acid, stearic acid, phenylstearic acid and peric acid; Unsaturated aliphatic groups such as ricinolic acid, ricinolbellad acid and 9-oxy-12-octadecenoic acid.

Examples of aliphatic esters as component G include aliphatic monohydric alcohol esters such as methyl phenylstearate and butyl phenylstearate; And monohydric alcohol esters of polybasic acids such as phthalic acid diesters of phthalic acid diphenylstearyl. Other examples of the higher aliphatic esters are sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Sorbitan esters such as sorbitan monopalmitate, polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; Glycerin monomers such as monoglyceride stearate, monoglyceride oleate, monoglyceride caprinate and monoglyceride behenate; Aliphatic esters of polyglycerols such as polyglycerol stearate, polyglycerol oleate and polyglycerol laurate; Aliphatic esters having the same polyalkylene ether units such as polyoxyethylene monolaurate, polyoxyethylene monostearate and polyoxyethylene monooleate; And neopentylpolyol aliphatic esters such as neopentylpolyol distearic acid ester.

Examples of higher aliphatic amides as component G include monoamides of saturated aliphatic acids such as amide phenylstearate, amide methylolstearate and amide methylolbehenate; N, N'-2-substituted monoamides such as diethanolamide of coconut oil fatty acid and diethanolamide of oleic acid. Specific examples of the higher aliphatic amides include methylenebis (12-hydroxyphenyl) stearic acid ester, ethylenebisstearic acid amide, ethylenebis (12-hydroxyphenyl) stearic acid amide and hexamethylenebis (12-hydroxyphenyl) Saturated aliphatic bisamides such as stearic acid amide and aromatic bisamides such as m-xylenebis (12-hydroxyphenyl) stearic acid amide.

Examples of higher aliphatic alcohols as component G include monohydric alcohols such as stearyl alcohol and cetyl alcohol; Polyhydric alcohols such as sorbitol and mannitol; Polyoxyethylene dodecyl amide; And polyoxyethylene octadecylamine. Specific examples of the higher fatty acid alcohols include alkylated ethers having polyalkylene ether units such as polyoxyethylene alkylated ethers; Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene tridodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; And dihydric alcohols with polyalkylene ethers such as polyepichlorohydrin ether, polyoxyethylene bisphenol A ether, polyoxyethylene ethylene glycol, polyoxyethylene bisphenol A ether and polyoxyethylene polyoxyethylene glycol ether.

Metallurgical excursion as component G includes the above-mentioned higher aliphatic acids, such as stearic acid with metals such as barium, calcium, zinc, aluminum and magnesium.

The low volatile flame retardant for styrene resin of the present invention can be used together with the thermoplastic elastomer (component H) if necessary according to the type of the resin composition. Examples of such thermoplastic elastomers include polystyrene, polyolefins, polyesters, polyurethanes, 1,2-polybutadiene and polyvinyl chloride thermoplastic elastomers. Most preferred of these thermoplastic elastomers are polystyrene thermoplastic elastomers.

The amount of component H is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight and most preferably 2 to 5 parts by weight per 100 parts by weight of the rubber-modified styrene used.

The polystyrene thermoplastic elastomers described above are block copolymers or block copolymers of aromatic vinyl units and conjugated diene units, wherein the conjugated diene is partially hydrogenated.

Examples of the aromatic vinyl monomers constituting the above-mentioned block copolymers include styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene and 2,4,5-tribromostyrene. As the main component, styrene and the other aromatic vinyl monomers described above can be copolymerized.

Examples of conjugated dienes constituting the aforementioned block copolymers include 1,3-butadiene and isoprene.

The block structure of the block copolymer is represented by SB, S (BS) _n (where n is represented by an integer of 1 to 3) or S (BSB) _n (where n is represented by an integer of 1 or 2). Linear block copolymer or (SB) _n X (wherein n represents an integer of 3 to 6, X represents a coupling agent residue such as silicon tetrachloride, tin tetrachloride, and polyepoxy compound) Where the polymer block of aromatic vinyl units is represented by S and the conjugated diene and / or partially hydrogenated conjugated diene units are represented by B. Particularly preferred of these block structures are SB, SBS and SBSB linear block copolymers.

If light resistance is required, the low volatility flame retardant for the styrene resin of the present invention may be selected from ultraviolet light absorbers, suppressed amine light stabilizers, antioxidants, halogen-capturing agents, light blocking agents, metal deactivators, and light quenching if necessary according to the type of resin composition. It can be used in combination with one or more light resistance enhancers (component I) selected from the group consisting of the agents.

The amount of component I used is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight per 100 parts by weight of the styrene resin to be used.

As component I, the ultraviolet light absorber reduces the internal molecular protons to be a keto-type molecule (cyano acrylate) or cis-trans isomerization (cyano acrylate) to relieve it as thermal energy to absorb light energy and thereby It is a component that blocks. Examples thereof include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and 5,5'-methylenebis (2-methylenebis ( 2-hydroxybenzophenone, such as 2-hydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'- t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5 ' -Di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy 2,2'-hydroxyphenyl) benzo such as oxy-3 ', 5'-dicumylphenyl) benzotriazole, and 2,2'-methylenebis (4-t-octyl-6-benzotriazole) phenol Triazole, phenylsalicylate, resorcinol monobenzoate, 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate and hexadecyl-3 , 5-di-t-butyl-4-hydroxybenzoate Benzoates such as, 2-ethyl-2'-ethoxyoxanilides and substituted oxanilides such as 2-ethoxy-4'-dodecyloxanide, and ethyl-α-cyano-β, β Cyano acrylates such as -diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

The amine light stabilizer suppressed as component I is a component which decomposes hydrogen peroxide produced by light energy to produce stable N-O or N-OH to stabilize the resin composition. Specific examples of inhibited amine light stabilizers are 2,2,6,6, -tetramethyl-4-piperidylstearate, 1,2,2,6,6, -pentamethyl-4-piperidylstearate , 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6,6-tetramethyl-4-piperidyl sebacate, bis (1,2,3 , 6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxyl Tetra, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3 ′, 5′-di-t-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl- 4-pyrepidinool / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6- Bis (2,2 , 6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-t-octylamino-s-triazine polycondensate, 1,6-bis (2,2,6,6 -Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate.

As component I, an antioxidant is a component that stabilizes peroxide radicals, such as hydrogen peroxide radicals generated during thermoforming or light exposure, or decomposes peroxides such as hydrogen peroxide produced. Examples of such antioxidants include inhibited phenol oxidation inhibitors and peroxide degradants. The former acts as a radical chain terminator to inhibit spontaneous oxidation, while the latter decomposes peroxides produced in the system into alcohols which more stably inhibit spontaneous oxidation.

Specific examples of phenolic antioxidants inhibited as antioxidants include 2,6-di-t-butyl-4-hydroxyphenol, styrenated phenol, n-octadecyl-3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate, 2,2'- methylenebis (4-methyl-6-butylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5- Methylbenzyl) -4-methylphenylacrylate, 2- (1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl) -4,6-di-t-pentylphenylacrylate, 4, 4′-butylidenebis (3-methyl-6-t-butylphenol), 4,4′-thiobis (3-methyl-6-t-butylphenol), alkylated bisphenols, tetrakis (methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, 3,9-bis (2- (3- (3-t-butyl-4 -hydroxy-5-methylphenyl) -Propionyloxy) 1,1-dimethylethyl) -2,4,8,10-tetraoxyspiro (5 · 5) undecane.

Specific examples of peroxide decomposers as antioxidants include organic phosphorus peroxide decomposers such as trisnonyl phenyl phosphite, triphenyl phosphite and tris (2,4-di-t-butylphenyl) phosphite, and dilauryl-3 , 3'- thiodipropionate, dimyristyl-3,3'- thiodipropionate, distearyl-3,3'- thiodipropionate, pentaerythritol tetrakis (3-la Urylthiopropionate), ditridecyl-3,3'-thiodipropionate and 2-mercaptobenzimidazole.

Halogen-capturing agent as component I is a component that captures the free halogen produced during thermoforming or photoexposure. Specific examples of such halogen-capturing agents include basic metal salts such as calcium stearate and zinc stearate, hydrotalcite, zeolites, magnesium oxides, organic tin compounds, and organic epoxy compounds.

Examples of hydrotalcites as halogen-capturing agents include hydrated or anhydrous basic carbonates of magnesium, calcium, zinc, aluminum, bismuth. The hydrotalcite may be natural or synthetic. Examples of natural hydrotalcites include those represented by the structural formula Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O. Examples of synthetic hydrotalcite is _{Mg 0.7 Al 0.3 (OH) 2} (CO 3) 0.15 · 0.54H 2 O, Mg 4.5 Al 2 (OH) 13 CO 3 · 3.5H 2 O, Mg 4.2 Al 2 (OH) 12.4 CO ₃ , Zn ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O, Ca ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O, and Mg ₁₄ Bi ₂ (OH) _29.6 · 4.2H ₂ O .

Examples of the above-described zeolite is substituted by a metal containing at least one metal selected from the A-type zeolite, and the Group 2 and Group 4 of the group consisting of metals expressed as _{Na 2 O · Al 2 O 3} · 2SiO 2 · H 2 O Included zeolites. Examples of substituent metals include Mg, Ca, Zn, Sr, Ba, Zr and Sn. Particularly preferred among these substituent metals are Ca, Zn and Ba.

Examples of the epoxy compound described above as the halogen-capturing agent include epoxidized soybean oil, tris (epoxy propyl) isocyanurate, hydroquinone diglycidyl ether, diglycidyl ester terephthalate, 4,4′-sulfobisphenolpoly Glycidyl ether, N-glycidyl phthalimide, hydrogenated bisphenol A glycidyl ether and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclo Hexylspiro [5,5] -3,4-epoxy (cyclohexane-m-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexane carboxylate, methylenebis (3,4 -Epoxycyclohexane), dicyclopentadiene epoxide, di (3,4-epoxycyclohexylme of ethylene glycol) ) Include alicyclic epoxy compounds, such as ether, ethylene bis (3,4-epoxy cyclohexanecarboxylate), dioctyl epoxy hexahydrophthalate, and di-2-ethylhexyl epoxy hexahydrophthalate.

As component I, the light blocking agent is a component which prevents the inside of the high molecular compound from reaching. Specific examples of light blocking agents include rutile titanium compounds (TiO ₂ ), zinc oxide (ZnO), chromium oxide (Cr ₂ O ₃ ), and cerium oxide (CeO ₂ ).

As component I, the metal deactivator is a component that inactivates heavy metal ions in the resin to produce shellate. Specific examples of metal deactivators include acid amine derivatives, benzotriazoles, and derivatives thereof.

As an constituent I, the photodecaying agent is a component which inactivates functional groups such as hydrogen peroxide and carbonyl groups which are optically excited in the polymer compound by transition energy. Organic nickel is known as the photodecaying agent.

One of the preferred compounds constituting the low volatile flame retardant for the styrene resin of the present invention is the flame retardant represented by the formula (I) in an amount of 3 to 30 parts per 100 parts by weight of the styrene resin used, wherein a, b and c each independently represent an integer of 1 to 3; at least one of R ₁ , R ₂ and R ₃ represents an isopropyl group or an aryl group, and other R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or In the substituents represented by halogen-free alkyl groups, R ₁ , R ₂ and R ₃ , which are not isopropyl groups, the total carbon number is 12 to 25 on average in one molecule of aromatic phosphate, provided that the flame retardant is A plurality of aromatic phosphates having different substituents, the total number of carbon atoms in the substituents R ₁ , R ₂ and R ₃ of the flame retardant is expressed as the number average of the total flame retardant, and the production of the weight fraction of the individual aromatic phosphates Water and the sum of the total number of carbon atoms in the substituents in the individual aromatic phosphates), and tris (nonylphenyl) phosphate (2) (wherein R ₁ , R ₂ and R ₃ in formula (I) are each nonyl groups) And dimerization and trimerization products of the aromatic vinyl monomer and the aromatic vinyl monomer remaining in the resin composition, up to 1% by weight. The flame retardant resin composition is preferably a dropwise flame retardant resin composition.

The flame retardant wherein at least one substituent R ₁ , R ₂ and R ₃ is an isopropyl group is a flame retardant, all of its alkyl groups such as nonylphenyl groups except for only one isopropyl group, so long as the total number of carbon atoms in the substituent meets the above requirements It may be a flame retardant or a flame retardant having 4 to 8 isopropyl groups in all.

Flame retardants in which one or more substituents R ₁ , R ₂ and R ₃ are aryl groups, non-flame retardants, their substituents being nonyl except for one aryl group such as phenyl groups, benzyl groups and dense groups, so long as the total number of carbon atoms in the substituents meets the above requirements Flame retardants which are all alkyl groups, such as phenyl groups, or flame retardants having a plurality of aryl groups described above in all. Particularly preferred among the aforementioned aryl groups are phenyl group, benzyl group, and gumyl.

In the preferred mixing of the resin composition of the present invention, it is important that the total content of the dimerization and trimerization products of the aromatic vinyl monomer and the vinyl aromatic monomer (hereinafter, residual monomer and oligomer) remaining in the resin composition is 1% by weight or less. The aforementioned residual monomers and oligomers act as fuel during combustion, weakening the flame retardancy of the resin composition. The flame retardant selected from at least one R ₁ , R ₂ and R ₃ isopropyl group and / or aryl group, and tris (nonylphenyl) phosphate is up to 50% by weight at 400 ° C. Monomeric aromatic phosphates according to the main aspects of the invention such as bis (nonylphenyl) phenylphosphate have a volatilization loss of at least 50% by weight under the same conditions as mentioned above. In enemy flame retardation mechanisms, the flame retardancy depends on the volatilization loss of the flame retardant in the weather. Flame retardants having a volatilization loss of at least 50% by weight at 400 ° C. exhibit excellent flame retardancy during combustion and are therefore not significantly affected by the flame retardancy of the aforementioned residual monomer and oligomer contents. However, the inventors of the present invention found that the aromatic phosphate in the flame retardant having low volatility at 400 ° C. is greatly influenced by the content of the above-described residual monomers and oligomers. It has been shown that it indicates a dramatic improvement. This fact is not known so far and cannot be foreseen even from common knowledge. Since the mechanism is unknown, bulky groups such as isopropyl groups, hard and dry groups such as aryl groups, or monomeric aromatic phosphates having a total number of carbon atoms in their substituents, such as tris (nonylphenyl) phosphate, exceeding 25 are extremely low volatility at 400 ° C. This results in the volatilization loss of the above-mentioned residual monomer and oligomer, which exceeds the loss of the flame retardant described above, thus weakening the flame retardancy of the resin composition.

In view of improving heat resistance, the preferred mixture constituting the low volatile flame retardant for the styrene resin of the present invention is polyphenylene in an amount of 1 to 10 parts by weight, preferably 3 to 8 parts by weight, per 100 parts by weight of the resin composition used. A dropwise flame retardant resin composition consisting of an ether and a flame retardant selected from the group consisting of flame retardants (1) and (2) described above in an amount of 1 to 20 parts by weight per 100 parts by weight of the resin composition used, wherein the aromatic vinyl monomer remaining in the resin composition and The dimerization and trimerization products of aromatic vinyl monomers are up to 1% by weight.

In terms of providing better dropping properties, the preferred compounds constituting the low volatile flame retardant for styrene resins of the present invention are 1 to 10 weight per 100 parts by weight of styrene resin having a viscosity η SP / C of 0.4 to 0.6 dl / g. Part, preferably 3 to 8 parts by weight of the dropwise flame retardant resin composition consisting of polyphenylene ether having a reduced viscosity of 0.3 to 0.6 dl / g, and 1 to 20 parts by weight per 100 parts by weight of styrene resin One flame retardant (1) A flame retardant selected from the group consisting of (2), and the dimerization and trimerization products of the aromatic vinyl monomer and the aromatic vinyl monomer remaining in the resin composition are 1% by weight or less.

An example of a method for producing a resin composition composed of preferred compounds constituting the low volatile flame retardant for styrene resins of the present invention is to dissolve rubber-modified styrene resins and other thermoplastic resins, add the flame retardant of the present invention to the resin, and then A process consisting of dissolving-kneading the mixture through the same extruder; A method comprising preparing a master batch made of styrene resin, other thermoplastics, and optionally the flame retardant of the present invention, and then kneading the master batch with the styrene resin residue or the flame retardant or other flame retardant of the present invention.

In particular, as a production method using polyphenylene ether as the thermoplastic resin, the following method is preferable to be used.

One of the methods for producing a low volatile flame retardant for styrene resins and a resin composition composed of polyphenylene ether as an essential component is to divide the styrene resin into two batches, and to separate the styrene resin and polyphenylene ether from the first resin composition. Preparing a first resin composition consisting of one of two batches in an amount of at least 50% by weight based on the amount, dissolving the resin composition at a temperature of 250 ° C. to 350 ° C. in the previous stage of the twin-screw extruder, and The composition consists of dissolving and extruding at a temperature of 200 ° C. to 300 ° C. in a later stage of the twin-screw extruder together with the other two batches of styrene resin and the second resin composition consisting of the flame retardant according to the invention.

In the above method, the resin composition composed of styrene resin and polyphenylene ether dissolved in the previous stage of the twin-screw extruder has a polyphenylene ether content of at least 50% by weight. If the polyphenylene ether content falls below 50% by weight, no shear force is applied to the resin composition, resulting in a product of undissolved polyphenylene ether.

Preferably, the resin composition and the flame retardant are separated from each other upon dissolution-mixing of the resin composition. Dissolving the resin composition in the presence of a flame retardant produces undissolved material due to the large difference in viscosity between the two components. More specifically, the resin composition consisting of styrene resin and polyphenylene ether having a polyphenylene ether content of 50% by weight or less is dissolved at a temperature of 250 ° C to 350 ° C.

Subsequently, the resin composition and the residue of the flame retardant of the present invention are dissolved at a temperature of 200 ° C to 300 ° C.

Dissolving the resin composition containing the polyphenylene ether at a temperature below 250 ° C. produces undissolved polyphenylene ether. When the resin composition consisting of polyphenylene ether is dissolved at a temperature of 350 ° C. or higher, the styrene resin starts to decompose. When the flame retardant of the present invention is dissolved at 200 ° C. or lower, the miscibility of the resin composition and the flame retardant is reduced, causing phase separation of the flame retardant, and therefore, it is difficult to perform stable extrusion. If the flame retardant is melted at 300 ° C. or higher, the flame retardant may adversely evaporate or decompose.

In the method for producing a resin composition composed of a low volatile flame retardant for styrene resins of the present invention, the twin-screw extruder preferably has an L / D ratio of 20 to 50 (D represents the inner diameter of the cylinder and L represents the length of the screw). And a plurality of supply openings including a main supply opening and a sub supply opening, each positioned at a different distance from the end of the twin-screw extruder, and the kneading zone is between the plurality of supply openings and the end of the twin-screw extruder and Located between the feed openings closest to the end of the twin-screw extruder, the kneading zones each have a length of 3D to 10D.

Firstly, the aforementioned L / D ratio is preferably 20 to 50. If L / D is 20 or less, the dissolution kneading property becomes poor, resulting in undissolved polyphenylene ether. If the L / D exceeds 50, the residence time of the resin composition in the extruder is extended, enabling the weakening of the resin composition.

Secondly, the twin-screw extruder preferably has two or more feed openings with different distances from their ends. With only one feed opening, the polyphenylene ether with high melt viscosity and the flame retardant of the present invention with low melt viscosity are phase separated. Thus, at least two supply openings are preferably provided. More specifically, after dissolving the resin composition in the main supply opening, the raw material of the flame retardant of the present invention is dissolved through the secondary supply opening.

Third, it is preferably between the main feed opening and the sub feed opening and between the end of the compressor and the sub feed opening, and the length of the kneading zone is preferably 3D to 10D, respectively. If the length of the kneading zone falls below 3D, the dissolution kneading conditions are poor, resulting in vented or undissolved polyphenylene ether. If the length of the kneading zone exceeds 10D, the residence time of the resin composition in the extruder is extended to weaken the resin composition. In addition, in the case where a plurality of sub feed openings are provided, it is necessary to knead the kneading zone between the main feed opening and the sub feed openings, between the other sub feed openings, and between the end and the sub feed openings of the extruder.

Fourth, the kneading zone of the twin-screw extruder is a zone for improving the kneading and mixing conditions. It is one of (1) a fully movable screw zone, (2) reverse screw zone and (3) a kneading disc or kneading block with special mixing components.

The full actuation screw consists of a special mixing element 1 consisting of a dulmage screw, a slotted mixing section, a single mixing screw, a spiral shield screw, a pin screw, a pineapple mixer and a co-transmission mixer.

The reverse screw zone 2 acts to suppress the flow of resin and thus generates a back pressure to provide great kneading ability.

Bonding zones 3, called kneading discs or kneading blocks, are ellipsoids that are inclined to some degree. This is because the bonding of the ellipsoidal disks inclined at 90 ° C to each other has excellent kneading ability, not screw force. The combination of elliptical discs tilted forward at 30 ° C with each other has a slight screw force but also a small kneading ability. In addition, the thickness of the disk can be changed. The larger the thickness of the disk, the smaller its mixing ability, but the better the kneading degree and shearing ability. The larger the thickness of the disk, the greater the screw force and mixing capacity, but the smaller the kneading capacity.

The shape of the kneading disc may be a triangular triple woven disc or a double woven disc. Triple woven discs provide excessive shear forces but have much more chances of branching / bonding in the interlocked areas, providing excellent distribution and mixing properties. Double weave discs have a smaller shear force than triple weave discs.

The kneading disc can be adjusted in mixing and kneading properties by varying the shape, angle position, amount and thickness thereof.

Fifth, the twin-screw extruder described above is a twin-screw non-directional rotary extruder or twin-screw two-way rotary extruder. The two extruders can be interlocked, partially interlocked or all interlocked. In the case where low shear forces are applied to obtain a homogeneous resin at low temperatures, two-way rotating partially engaged screws are preferred. If some large kneading ability is required, non-directional rotating all-engaged screws are preferred. Where greater kneading ability is required, non-directional rotating all-engaged screws are preferred.

The most preferable method for producing a resin composition composed of a low volatile flame retardant for styrene resin of the present invention is to prepare a master batch consisting of a polyphenylene ether and a resin composition consisting of the flame retardant of the present invention, or as the essential components, the resin composition and styrene described above. A master batch consisting of a resin and / or rubber-modified styrene resin is prepared, adding residues of the components of the final resin composition to the master batch to produce a mixture, which is then dissolved-kneaded. The glass transition temperature (Tg) of the master batch is 70 ° C to 100 ° C.

It is desirable to prepare the master batch described above. It is possible to dissolve and knead all of the aforementioned components simultaneously without producing the master batch described above, or to prepare a plurality of zones in a resin composition composed of polyphenylene ether, a flame retardant, and a styrene resin or a resin composition composed of polyphenylene ether or a flame retardant. If dissolved by means of an extruder having, as a result, residues of styrene resin or flame retardant are melt-extruded, and a flame retardant of polyphenylene ether having a high melt viscosity is produced or a flame retardant which is easily phase separated is ejected into the extruder, Extrusion stability is reduced. Thus, polyphenylene ethers with high melt viscosities, flame retardants with low melt viscosities, and optionally styrene resins, can be used to prepare master batches that answer the above-mentioned problems.

The glass transition temperature (Tg) of the aforementioned master batch is preferably 70 ° C to 100 ° C. If the Tg exceeds 100 ° C., the master batch does not dissolve completely in the presence of styrene resins and flame retardants with low dissolution viscosities resulting in reduced costly polyphenylene ether or impact strength. In particular, the impact strength changes depending on the kneading conditions. Conversely, if the Tg falls below 70 ° C., the master batch exhibits reduced extrusion capacity when blocking the hopper or feeding to the extruder. Thus, the preparation of certain master batches described above maintains sufficient extrusion stability and high productivity and improves impact strength, heat resistance, melt flowability and appearance, even if phase separation of the flame retardant is suppressed to increase the amount released during subsequent melt extrusion. Makes it possible to let.

Preferred examples of the resin composition composed of the low volatile flame retardant for the styrene resin of the present invention are 100 parts by weight of a styrene resin (component B) consisting of 30 to 70 parts by weight of the rubber-modified styrene resin and 30 to 70 parts by weight of the unmodified styrene resin. Monomer alkyl-substituted aromatic phosphates and polydimethylsiloxanes (component D) consisting of polyphenylene ether (component C), NPDP, BNPP and TNPP (component A) in an amount of 3 to 8 parts by weight and 0.1 to 2 parts by weight per part to be.

The above-mentioned compositions have good balance of flame retardancy, in particular dropwise flame retardancy, continuous molding properties, moldability (dissolution flowability), impact strength, heat resistance and surface hardness, and water-resistant gloss retention of the molded article.

The resin composition composed of the low volatile flame retardant for the styrene resin of the present invention can be obtained by dissolving and kneading by, for example, a commercial single-screw extruder or a twin-screw extruder by carrying out the various components described above. During this procedure, if necessary, oxidation of the system such as phenol inhibited, ultraviolet absorbers such as benzotriazole and inhibited amines, tin heat stabilizers, inorganic or halogen flame retardants, lubricants such as stearic acid and zinc stearate, fillers, Reinforcing agents, such as glass fibers, and coloring agents, such as dyes and pigments, may be added.

The obtained composition can be molded by an injection molding machine or an extruder to extend the time continuously. The molded product obtained is excellent in flame retardancy (dropping flame retardancy), heat resistance and impact resistance.

EXAMPLE

The invention is described in more detail in the following examples and comparative examples, but the invention is not reduced or limited thereto.

In the following examples and comparative examples, various measurements were made by the following measuring methods and measuring instruments:

(1) Analysis of flame retardant and resin composition

(A) 5 g of the resin composition was dissolved in 100 ml of methyl ethyl ketone and then separated by ultracentrifuge (20,000 rpm, 1 hour). As a result, methanol was added to the supernatant in twice the amount of the supernatant so that the resin component was separated. The solution portion and the resin portion were each separated by an ultracentrifuge. Solution part GPC (gel permeation chromatography) (commercially available from Toso Co., Ltd .; chromatography apparatus (with RI segment indicator detector): HLC-8020; column: commercially available from Toso Co., Ltd .; G1000HXL (2 sets used) Mobile phase: tetrahydrofuran; flow rate: 0.8 ml / min; pressure: 60 kgf / cm ² ; temperature: 35 ° C. (oven), 40 ° C. (oven), 35 ° C. (RI); sample loop: 100 ml; Injection amount of the sample: 0.08 g / 20 mL). If the area ratios of the various components on the chromatography were weight fractions of the various components, the dimerization and trimerization products of the phosphate and composition and the remaining aromatic vinyl monomers and the aromatic vinyl monomers were determined from the area ratios. The resin portion was measured for the integration ratio of the aromatic portion and the aliphatic portion by a Fourier inverted nuclear magnetic resonance device (proton-FT-NMR). Thus the amount of rubber modified or unmodified styrene resins and thermoplastic resins such as aromatic polycarbonates and polyphenylene ethers were measured.

(B) acid value of flame retardant

The flame retardant was measured for acid values according to JIS-K6751 as a measure of the amount of acidic substance remaining therein.

(C) coloring tint of flame retardant

The flame retardant was measured by the Gardner method according to the "Reference Fats and Oils Analysis Method" established by Society of Oil Chemistry of Japan. The smaller the Gardner standard color reading, the thinner the coloring tint.

(D) light resistance of flame retardant

To evaluate the light resistance, 30 g of flame retardant was filled in a 50-ml glass bottle. Next, the sample was taken from Shimadzu Corp. It was kept for 10 days in SUN TESTER XF-180 (light source: xenon lamp) which is commercially available. The percent change in color tone and the acid value before and after the test were measured as an indicator of light resistance.

(E) Heat discoloration resistance of flame retardant

In order to evaluate the heat discoloration resistance, 30 g of flame retardant was filled in a 50-ml glass bottle. The sample was kept at 300 ° C. for 1 hour. The percent change in color hue was then measured as an indicator of heat decolorization resistance.

(F) viscosity of flame retardant

The flame retardant was measured at a temperature of 25 ° C. using a Brookfield type viscometer commercially available from Brookfield Engineering Laboratories, Inc. (Stoughton, Massachusettes, USA).

(G) Residual amounts of aluminum, magnesium, sodium and antimony in flame retardants

To determine the residual amounts of aluminum, magnesium, sodium and antimony in flame retardants, flame retardants are described in “Encyclopedia of Chemical Technology”, Third Edition, Volume 2, 'Atomic Absorption and Emission Spectroscopy', pp. 621-623, 591, 155 , 156, A Wiley-Interscience Publication, John Wiley & Sons, New York, 1978, were analyzed by atomic absorption spectroscopy.

(H) volatility of flame retardants

Flame Retardant Shimadzu Corp. Heated at a rate of 40 ° C./min in a nitrogen stream by a DT-40 thermal analyzer commercially available. Heat loss at 300 ° C or 400 ° C was measured by measuring volatilities (thermogravimetric analysis test: TGA method).

The flame retardant was allowed to stand for 5 minutes at 250 ° C. in a nitrogen stream using the same apparatus as mentioned above. The resulting residue was measured by measuring other volatilities.

(2) weight-average particle diameter of the rubber-modified styrene resin

In order to measure the weight-average particle diameter of the rubber-modified styrene resin, the diameter of the rubber particles (butadiene polymer particles) was measured on a transmission electron microscope of the ultrathin portion of the resin composition. The weight-average particle diameter of the rubber-modified styrene resin was calculated from the following formula:

Weight-average particle diameter = Σ NiDi4 / Σ NiDi3

(Di represents the measured particle diameter of the butadiene polymer particles, Ni represents the number of measured butadiene polymer particles having a particle diameter of Di).

(3) Converted viscosity of rubber-modified styrene resin and polyphenylene ether η Sp / C

To 1 g of rubber-modified styrene resin was added a mixture of 18 ml of methyl ethyl ketone and 2 ml of methanol. The mixture was then shaken at 25 ° C. for 2 hours. The mixture was then centrifuged at 5 ° C. at 18,000 rpm for 30 minutes. The supernatant was recovered. The resin contents were precipitated with methanol and dried.

The obtained 0.1 g of the resin was dissolved in toluene for rubber-modified polystyrene resin or methyl ethyl ketone for rubber-modified acrylonitrile-styrene copolymer resin to make a 0.5 g / dl solution. The 10 ml solution obtained above was then charged to a Kenon-Penske Viscometer. The solution was measured at 30 ° C. with dropping time T ₁ (seconds).

Pure toluene or pure methyl ethyl ketone was measured at dropping time T ₀ (seconds) using the same viscosity meter. Next, the converted viscosity η Sp / C (wherein C represents the resin concentration (g / dl)) was measured from the following formula:

η Sp / C = {(T ₁ / T ₀ ) -1} / C

To evaluate the equivalent viscosity η Sp / C of the polyphenylene ether, 0.1 g of polyphenylene ether was dissolved in chloroform to make a 0.5 g / dl solution measured in the same manner as described above.

(4) Izod impact strength

Izod impact strength is measured at a temperature of 23 ° C. in accordance with ASTM-D256 with a V-notch and a 1/8 inch test piece.

(5) fallout impact strength

Fall impact strength is measured at a temperature of 23 ° C. in a similar manner to ASTM-D1709. Specifically, a DuPont impact tester (manufactured by TOYO SEIKI SEISAKUJO K.K.) is used. A dart (weight: 200 g) having a diameter of 9.5 mm and a length of 5.2 mm at the apex of the impact center is in contact with the surface of the molded part (70 mm square; 2 mm thick) on a pad of 9.5 mm diameter and 4.0 mm depth of hole. . The rod is dropped on the molded part at a height of up to 50 cm. The load weight at which 50% of the molded part is destroyed is defined as 50% breaking rod. The 50% breaking energy is then calculated as the fall impact strength by multiplying the 50% breaking rod by the weight of the falling rod (unit: kgcm).

(6) strength

Flexural modulus is measured according to ASTM-D790 as a measure of strength.

(7) tensile strength and tensile strength

Tensile strength and tensile elongation are measured according to ASTM-D638.

(8) heat deflection temperature

The heat deflection temperature is measured according to ASTM-D648 as a measure of heat resistance (test rod: 18.5 kg / cm ² ; 1/4 inch thickness test piece).

(9) non-cat softening temperature

Non-cat softening temperature is measured according to ASTM-D1525 as a measure of heat resistance.

(10) Melt Flow Rate (MFR)

Melt flow rate is measured according to ASTM-D1238 as an index of the melt flow. The extrusion rate (g / 10 min) for 10 min at a load of 5 kg and a dissolution temperature of 200 ° C. is determined.

(11) glossiness

To evaluate the gloss, the mirror gloss at a 60 degree throw angle is determined according to ASTM-D523.

(12) flame retardant

Flame retardancy is evaluated by the VB (Vertical Burning) method according to UL-subject 94 using 1/8 inch specimens.

For details of the method of UL-subject 94, reference may be made, for example, to US Pat. No. 4,966,814.

The exotherm rate is measured using ATLAS Corn Calorimeter II (manufactured by ATLAS Electric Devices Co.) according to ASTM-E1354. Measure at a radiant heat flux of 50 kW / m ² . Install the sample horizontally. The area of the sample is 0.006 m ₂ .

(13) Volatilization degree of resin composition (thermal weight analysis test: TGA method)

The resin composition is heated with a thermal analyzer DT-40 type (manufactured by Shimadzu Corp., Japan) at a rate of 10 ° C / min in a flow of nitrogen. The temperature at which the weight loss reaches 1% is determined as a measure of the volatility of the resin composition.

(14) Light resistance of the molded article

The light resistance test is performed using an ATLAS C135W weather tester (manufactured by ATLAS Electric Devices Co., USA) as a light resistance tester according to JIS K7102. The sample is spun into xenon light (wavelength: 340 nm; energy 0.30 W / m ² ) at a tester internal temperature of 55 ° C. and humidity of 55% without a shower for 300 hours. The color difference ΔE before and after the test was determined by Lab method using an SM-3 type SM color computer (Suga Shikenki Co., Japan) to evaluate the color change. The smaller the color difference, the higher the light resistance.

(15) Thermal contraction rate% of molded article of resin composition

The 1/8 inch thick molded article of the resin composition obtained by compression molding or injection molding is placed in a 170 ° C. hot air dryer for 15 minutes. Then, the heat shrinkage rate S (%) is calculated from the dimensional change of the molded article by the following equation:

S = {(L ₀ -L) × 100 / L ₀ }

(Wherein L ₀ represents the size before heating and L represents the size after heating).

(16) Water resistant gloss retention of molded articles

In order to evaluate the water resistance, the molded article is placed at a constant 80 ° C for 24 hours. The gloss change (ΔG) before and after the test is determined as an index of water resistance. The smaller ΔG is, the smaller the change in gloss caused by hot water.

(17) surface strength of molded parts

The molded article is measured by pencil hardness (pencil scratch value) according to JIS-K5400 as an index of the surface strength of the molded article.

(18) kneading

The following parameters are used to assess kneading.

Kneading Parameters = (Extrusion Factor) / (Circumferential Speed of Screw) = (Q / D ² ) / π ND

(Where Q represents the extrusion amount (kg / hr), N represents the screw rotational speed (rpm), and D represents the inner diameter of the cylinder (mm)).

(19) glass transition temperature (Tg)

The sample is heated to a temperature of 400 ° C. at a rate of 10 ° C./min in a nitrogen flow with a DT-40 type thermal analyzer (manufactured by Shimadzu Corp.). Glass transition temperature is measured by DSC method.

As each component used by the Example and the comparative example, the following component is used.

(a) Aromatic Phosphates (Component A)

(1) Triphenyl Phosphate (TPP)

Commercial aromatic phosphate (trade name: TPP (hereinafter referred to as “TPP”), manufactured by Daihachi Kagaku Kogyo Co., Ltd.) is used.

The total number of carbon atoms in the substituents of TPP is 0 on average and the phosphorus content is 9.5% by weight.

(2) oligomeric aromatic phosphates (fr-1)

Commercial oligomeric aromatic phosphates derived from Bisphenol A (trade name: CR741 (hereinafter referred to as “fr-1”) manufactured by Daihachi Kagaku Kogyo Co., Ltd.) are used. According to the GPC analysis, oligomeric aromatic phosphates were obtained by weight ratio of 84.7 / 13.02 / 2.3, TPP-A-dimer (n = 1) and TPP-A-oligomer (n≥2) and triphenyl phosphate (TPP) represented by the following formula. ). The phosphorus content is 9.4% by weight.

(3) Preparation of Monomer Alkyl-Substituted Aromatic Phosphates (FR-1)

287.3 parts by weight (molar ratio: 2.0) of nonylphenol and 0.87 parts by weight (molar ratio: 0.01) of aluminum chloride are dispensed into the flask. Then, 100 parts by weight (molar ratio: 1.0) of phosphorus oxychloride is added dropwise to the mixture at a temperature of 90 ° C for 1 hour. Then, 61.4 parts by weight (molar ratio: 1.0) of phenol was added to the obtained intermediate product to further cause the reaction. To complete the reaction, the reaction system is gradually heated to 180 ° C. to complete the esterification. The reaction product obtained is cooled and then washed with water to remove the catalyst and chlorine content to obtain a phosphate mixture (hereinafter referred to as "FR-1"). The mixture thus obtained is then analyzed by GPC (gel permeation chromatography; HLC-8020, manufactured by Toso Co., Ltd. (mobile phase: tetrahydrofuran)). As a result, the mixture contained bis (nonylphenyl) phenylphosphate (hereinafter referred to as "BNPP"), trisnonylphenyl phosphate (hereinafter referred to as "TNPP"), nonylphenyl di at a weight ratio of 77.8 / 11.3 / 8.4 / 2.5. Phenyl phosphate (hereinafter referred to as “NDPP”), and nonylphenol.

The total number of carbon atoms in the substituents is 17.9 on average (18 × 0.778 + 27 × 0.113 + 9 × 0.084 = 17.9) and the phosphorus content is 5.5% by weight.

The monomeric aromatic phosphate mixture (FR-1) is distilled off and then fractionated by liquid chromatography to give BNPP.

(4) Preparation of Various Monomer Alkyl-Substituted Aromatic Phosphates

While following the procedure for manufacturing FR-1, “ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY”, 3rd edition, Volume 2, “ALKYLPHENOLS”, p. Various alkylphenols or commercial alkylphenols obtained by the method described in 72-96 (A WILEY-INTERSCIENCE PUBLICATION, John Wiley & Sons, New York 1978) are used, and their molar ratios to phosphorus oxychloride synthesize various alkylphenols. To be adjusted. Purification of these alkylphenols is carried out by rinsing, distillation, or fractionation by liquid chromatography. Table 1 shows various alkylphenols.

(b) thermoplastic resin

(1) rubber-modified styrene resin (HIPS)

Polybutadiene ((cis-1,4 bond / trans-1,4 bond / vinyl-1,2 bond weight ratio = 95/2/3); trade name: Nipol 122 OSL, manufactured by Nihon Zeon Co., Ltd.) Dissolve in the mixture to make a uniform solution.

Polybutadiene 10.5 wt%

Styrene 74.2 wt%

Ethylbenzene 15.0 wt%

0.27 wt% of α-methylstyrene dimer product

t-butylperoxyisopropyl carbonate 0.03% by weight

The mixture is then fed to a stirred cereal four-stage reactor. Thus, the mixture was stirred at 190 rpm and temperature 126 ° C. on the first stage, 50 rpm and temperature 133 ° C. on the second stage, 20 rpm and temperature 140 ° C. on the third stage, and 20 rpm and 155 on the fourth stage. Polymerize at ℃. Subsequently, the obtained polymerization solution having a solid content of 73% is introduced into the devolatilization apparatus, whereby unreacted monomer and solvent are removed to obtain a rubber-modified styrene resin (hereinafter referred to as "HIPS-1"). The rubber-modified styrene resin thus obtained is then analyzed. As a result, the rubber-modified styrene resin had a rubber content of 12.1 wt%, a weight average particle diameter of 1.5 mu m and a converted viscosity η SP / C of 0.53 dl / g.

The amount of polymerization initiator and the chain transfer agent and the polymerization temperature are varied to produce rubber-modified styrene resins having different reduced viscosity η SP / C. The results are shown in Table 8.

In addition, various HIPSs having different rubber types, rubber contents, rubber weight average particle diameters and converted viscosity η SP / C are prepared. Specifically, following the above procedure, styrene-butadiene block copolymer (styrene / butadiene ratio = 40/60 (by weight), cis-1,4 bond / trans-1,4 bond / vinyl-1,2 bond weight ratio = 37/50/13) as rubber instead of butadiene, the stirring speed is changed to control the weight average particle diameter of the rubber and the amount of α-methylstyrene dimer product is changed to control the converted viscosity of the product. . This obtained HIPS exhibits a rubber content of 15.0 wt%, a rubber weight-average particle diameter of 0.34 μm and a converted viscosity η SP / C of the following: 0.68 dl / g (hereinafter referred to as “HIPS-7”).

The procedure for preparing HIPS-1 is as follows, but copolymer HIPS (hereinafter referred to as “MS-HIPS” and “BA-HIPS”, respectively) is prepared by replacing the portion of styrene with α-methylstyrene or butyl acrylate. The copolymerizable monomer (α-methylstyrene or butyl acrylate) content of MS-HIPS and BA-HIPS is 4% by weight.

(2) rubber-unmodified styrene resin

Coil a mixture of 80.0 parts by weight of styrene, 20 parts by weight of ethylbenzene, and 0.03 parts by weight of 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane as an initiator at a rate of 2.5 1 / hr The feed was continued into the type premix reactor and the reaction mixture was polymerized at a temperature of 150 ° C. for an average holding time of 2 hours at a polymer solid concentration of 48%. Subsequently, the polymerization solution is introduced into a 230 ° C devolatilization device, whereby unreacted monomer and solvent are removed to obtain polystyrene. The polystyrene thus obtained has a weight average molecular weight of 160,000 and a number average molecular weight of 76,000 (hereinafter referred to as "GPPS-2").

While following the above procedure, n-dodecyl mercaptan is added as a chain transfer agent or the polymerization temperature is raised to produce polystyrene with low molecular weight. The results are shown in Tables 9 and 12.

(3) rubber-modified copolymer styrene resin

78.0 parts by weight of styrene, 2.0 parts by weight of methacrylic acid, 20 parts by weight of ethylbenzene, 0.02 parts by weight of n-dodecyl mercaptan and 0.03 parts by weight of 1,1-bis (t-butylperoxy) -3,3 The mixture of, 5-trimethylcyclohexane is continuously fed into the coiled complete mixing reactor at a rate of 2.5 l / hr and the reaction mixture is polymerized at a temperature of 150 ° C. for an average holding time of 2 hours at 47% polymer solids concentration. . Subsequently, the polymerization solution is introduced into a 230 ° C. devolatilization device. The unreacted monomer and the solvent are removed to obtain a styrene-methacrylic acid copolymer. The copolymer thus obtained exhibits a styrene / methacrylic acid weight ratio of 96/4, a weight average molecular weight of 120,000 and a number average molecular weight of 63,000 (hereinafter referred to as “SMAA-3”).

Following the above procedure, a copolymer having high molecular weight is prepared by using methacrylic acid, male anhydride, α-methylstyrene, or butyl acrylate as a copolymerizable monomer and reducing the amount of ethylbenzene as solvent or raising the polymerization temperature. do. Although following the above procedure, the amount of n-dodecyl mercaptan used as the chain transfer agent is increased or the polymerization temperature is raised to produce a copolymer having a low molecular weight. In addition, the polymerization composition ratio is controlled by changing the ratio of components to be charged for polymerization. The results are shown in Table 9.

(4) Preparation of Polyphenylene Ether (PPE)

Thoroughly replace the interior of the stainless steel reactor with an oxygen blowing port at the bottom and a cooling coil and a stirring blade inside. Next, 8.75 kg of 2,6-k in a mixture of 54.8 g of copper bromide (II), 1,110 g of di-n-butylamine, and 20 liters of toluene, 16 liters of n-butanol and 4 liters of methanol A solution of silenol is charged to the reactor. The reaction mixture is then polymerized with stirring, while oxygen is blown into the reactor while the internal temperature is adjusted to 30 ° C. for 90 minutes. After completion of the polymerization, the separated polymer is recovered by filtration.

A methanol / hydrochloric acid mixture is added to the polymer thus obtained to decompose the residual catalyst in the polymer. The polymer is washed thoroughly with methanol and then dried to give a powdered polyphenylene ether (hereinafter referred to as “PPE-1”). The product has a reduced viscosity η SP / C of 0.41 dl / g.

Although following the above procedure, the amount of catalyst used and the polymerization time are adjusted during the preparation of the polyphenylene ether to produce polyphenylene ethers having different equivalent viscosity η SP / C. The results are shown in Table 10.

(5) aromatic polycarbonate (PC)

Commercial bisphenol A polycarbonate (Novalex 8025A, Mitsubishi Chemical Corp., Japan) (hereinafter sometimes referred to as "PC") is used.

(6) ABS resin (ABS)

Commercial ABS resins (acrylonitrile / butadiene / styrene = 26/14/60 (by weight)) (hereinafter sometimes referred to as “ABS”) are used.

(7) polyethylene (PE)

Commercially low density polyethylene is used.

(8) polypropylene (PP)

Commercially unmodified polypropylene is used.

(9) polyamide (PA)

Commercial polyamide 6 is used.

(10) Polyethylene Terephthalate (PET)

Commercial polyethylene terephthalate is used.

(c) polyorganosiloxane

Polydimethylsiloxanes with different kinematic viscosities (Shin-Etsu Silicone KF96 Series, Shin-Etsu Chemical Co., Ltd) are used as shown in Table 16.

(d) light resistance improver

(1) UV absorbers

Ciba Geigy Corp. Benzotriazole UV light absorber (hereinafter referred to as “UVA”) is used.

(2) hindered piperidine light stabilizers

Ciba Geigy Corp. Hindered piperidine light stabilizer (trade name: Tinuvin 770) (hereinafter referred to as “HALS”) is used.

(3) sunscreen

Commercial titanium oxide (TiO ₂ ) powder (Ishihara Sangyo Kaisha, Ltd .; average size: 0.2 μm) (hereinafter referred to as “TiO ₂ ”) is used.

(4) antioxidant

Ciba Geigy Corp. Antioxidant (trade name: Irganox 1076 (hereinafter referred to as "AO")) is used.

(e) flame retardant

(1) Tetrabromobisphenol A epoxy oligomer (hereinafter referred to as "BEO") is used as the halogenated bisphenol type epoxy resin.

(2) antimony trioxide

Commercial antimony trioxide (hereinafter referred to as “Sb ₂ O ₃ ”) is used as auxiliary flame retardant.

The styrene resins used in the following examples, comparative examples and tables are summarized as follows.

[HIPS: Rubber-Modified Polystyrene]

HIPS-1: polybutadiene rubber-modified polystyrene with a rubber content of 12.1 wt%, a rubber weight average particle diameter of 1.5 μm and a converted viscosity η SP / C of 0.53 dl / g

HIPS-2: polybutadiene rubber-modified polystyrene with a rubber content of 12.1 wt%, a rubber weight average particle diameter of 1.5 μm and a converted viscosity η SP / C of 0.79 dl / g

HIPS-3: polybutadiene rubber-modified polystyrene with a rubber content of 12.1 wt%, a rubber weight average particle diameter of 1.5 μm and a converted viscosity η SP / C of 0.60 dl / g

HIPS-4: polybutadiene rubber-modified polystyrene with a rubber content of 12.1 wt%, a rubber weight average particle diameter of 1.5 μm and a converted viscosity η SP / C of 0.58 dl / g

HIPS-5: polybutadiene rubber-modified polystyrene with a rubber content of 12.1 wt%, a rubber weight average particle diameter of 1.5 μm and a converted viscosity η SP / C of 0.40 dl / g

HIPS-6: polybutadiene rubber-modified polystyrene with a rubber content of 12.1 wt%, a rubber weight average particle diameter of 1.5 μm and a converted viscosity η SP / C of 0.35 dl / g

HIPS-7: styrene-butadiene rubber (styrene / butadiene ratio = 40/60 (by weight)) with a rubber content of 15.0% by weight, a rubber weight average particle diameter of 0.3 μm and a converted viscosity η SP / C of 0.68 dl / g ) -Modified Polystyrene

[GPPS: Rubber-Unmodified Polystyrene]

GPPS-1: rubber-modified polystyrene having a weight average molecular weight of 212,000 and a number average molecular weight of 87,000

GPPS-2: rubber-modified polystyrene with weight average molecular weight of 160,000 and number average molecular weight of 76,000

GPPS-3: rubber-unmodified polystyrene having a weight average molecular weight of 135,000 and a number average molecular weight of 71,000

GPPS-4: rubber-unmodified polystyrene having a weight average molecular weight of 101,000 and a number average molecular weight of 59,000

[SMAA: Styrene-Methacrylic Acid Copolymer]

SMAA-1: styrene / methacrylic acid = 92/8 (by weight)

Weight average molecular weight: 200,000; Number average molecular weight: 85,000

SMAA-2: Styrene / Methacrylic Acid = 93/7 (by weight)

Weight average molecular weight: 110,000; Number average molecular weight: 55,000

SMAA-3: styrene / methacrylic acid = 96/4 (by weight)

Weight average molecular weight: 122,000; Number average molecular weight: 63,000

[SMA: Styrene-maleic Anhydride]

SMA-1: Styrene / maleic anhydride = 92/8 (by weight)

Weight average molecular weight: 248,000; Number average molecular weight: 113,000

SMA-2: Styrene / maleic anhydride = 85/15 (by weight)

Weight average molecular weight: 203,000; Number average molecular weight: 97,000

[Examples 1 to 5 and Comparative Examples 1 to 6]

The various monomeric aromatic phosphates shown in Table 1 are left to stand in a nitrogen stream for 5 minutes at a temperature of 250 ° C. and then measured by the residual amount by thermogravimetric analysis test. The results are shown in Table 1 and FIG. Table 1 and Figure 1 show that monomer aromatic phosphates having an average of at least 12 of the total number of carbon atoms in the substituents R ₁ , R ₂ and R ₃ exhibit excellent non-volatility.

TABLE 1

[Examples 6 to 10 and Comparative Examples 7 to 13]

The HIPS-1, GPPS-1 and aromatic phosphates shown in Table 2 are mechanically mixed in a ratio of 70/30/7 (by weight). The mixture was then added to Toyo Seiki Seisakujo K.K. Dissolve at a temperature of 50 rpm and 220 ° C. for 5 minutes in a laboplastomill available at. The resin composition thus obtained is then subjected to extrusion to prepare a 1/8 inch thick swatch for evaluating flame retardancy. The specimen thus obtained is then measured according to the above measuring method for the dimerization of the residual styrene monomer and styrene (residual monomer and oligomer) and the total content of the trimerization product. As a result, the above residual monomers and oligomers are detected in amounts of 1.1 to 1.5% by weight of all specimens. In addition, TPP, fr-1, and BNPP are heated at a rate of 40 ° C./minute in a nitrogen stream. The relationship between temperature and weight loss is determined by thermogravimetric testing. The results are shown in Table 2 and FIG.

Tables 2 and 2 show that samples having an average number of 12 to 25 carbon atoms in the substituents of aromatic phosphates show an excellent balance between flame retardancy and volatility.

As compared to monomeric aromatic phosphates, oligomeric aromatic phosphates exhibit low volatility and reduced flame retardancy at 400 ° C. at the initial stage of combustion. In addition, specific monomeric alkyl substituted aromatic phosphates stay non-volatile at molding temperatures below 300 ° C. and evaporate effectively at the initial stage of combustion, providing excellent flame retardancy.

TABLE 2

[Examples 11 to 14 and Comparative Examples 14 to 17]

The resin composition of Table 3 and BNPP are processed by the method similar to Example 6, and the sample for evaluating a flame retardance is produced. The results are shown in Table 3. According to the above measuring method, the specimen thus obtained is measured for the dimerization of the residual styrene monomer and the styrene (residual monomer and oligomer) and the total content of the trimerized product. As a result, the above residual monomers and oligomers are detected in amounts of 1.1 to 1.5% by weight of all specimens.

TABLE 3

[Examples 15 to 18 and Comparative Examples 18 to 25]

The composition obtained by combining the aromatic phosphate of Table 4 with 100 parts by weight of a styrene resin (including a 70/30 mixture of HIPS-1 and GPPS-1) was processed in the same manner as in Example 6 to obtain MFR, Izod (Izod). ) Samples are prepared to evaluate impact strength, Vicat softening temperature and flame retardancy. The results are shown in Table 4 and in Figures 3 and 4. According to the above measurement method, the specimen thus obtained is measured for residual styrene monomer and total content of dimerization and trimerization products of styrene. As a result, the above residual monomers and oligomers are detected in amounts of 1.1 to 1.5% by weight of all specimens.

Tables 4 and 3 and 4 show that the aromatic phosphate (BNPP) of the present invention shows an excellent balance between flame retardancy and physical properties, but TNPP and oligomeric aromatic phosphate (fr-1) are used in the same amount of reduced flame retardancy (BNPP). And heat resistance and impact strength (if used in larger quantities).

TABLE 4

[Examples 19 and 20 and Comparative Examples 26 and 27]

The monomeric aromatic phosphates shown in Table 5 are tested for light resistance according to the test method above. The results are shown in Table 5.

Table 5 shows that the monomeric aromatic phosphate containing isopropyl group has high viscosity, and shows the acid value change and large color tone in the light resistance test.

TABLE 5

[Examples 21 to 23 and Comparative Examples 28 and 29]

The composition obtained by combining the aromatic phosphate of Table 6 with 100 parts by weight of a styrene resin (including a mixture of 70/30 of HIPS-1 and GPPS-1) was processed in the same manner as in Example 6 to obtain MFR, Izod impact strength, Samples are prepared to evaluate the non-cat softening temperature and flame retardancy. The results are shown in Table 6. According to the above measuring method, the specimen thus obtained is measured for the dimerization of the residual styrene monomer and the styrene (residual monomer and oligomer) and the total content of the trimerization product. As a result, the residue is detected in an amount of 1.1 to 1.5% by weight of all specimens.

Table 6 shows that the monomer phosphate having a plurality of aromatic rings substituted by only one alkyl group is better in heat resistance than the monomer phosphate having only one aromatic ring substituted by only one long chain alkyl group.

In addition, aromatic phosphates containing hydroxyl groups can have excellent heat resistance.

TABLE 6

[Examples 24 to 33]

Monomer aromatic phosphates obtained under different purification conditions during the purification of FR-1 for separation of BNPP (shown in Table 7) are tested for thermal discoloration resistance according to the above method.

The composition obtained by combining the aromatic phosphate of Table 7 with 100 parts by weight of a styrene resin (including a mixture of 70/30 of HIPS-1 and GPPS-1) was processed in the same manner as in Example 6 to obtain MFR, Izod impact strength. Samples are prepared to evaluate the non-cat softening temperature and flame retardancy. The results are shown in Table 7. According to the above measuring method, the specimen thus obtained is measured for the dimerization of the residual styrene monomer and the styrene (residual monomer and oligomer) and the total content of the trimerization product. As a result, the residue is detected in an amount of 1.1 to 1.5% by weight of all specimens.

Table 7 shows that the higher the amount of residual aluminum and nonylphenyl as starting materials or the higher the acid value, the easier the thermal discoloration of the resin composition and the lower the flame retardancy and its heat resistance. The use of hindered phenol oxidation inhibitors can provide an improvement in thermal discoloration resistance.

TABLE 7

[Examples 34 to 39]

A composition obtained by combining 6 parts by weight of BNPP and 100 parts by weight of HIPS having a converted viscosity η SP / C in Table 8 was processed in the same manner as in Example 6 to evaluate MFR, Izod impact strength, non-cat softening temperature and flame retardancy. Prepare samples for

The results are shown in Table 8. According to the above measuring method, the specimen thus obtained is measured for the dimerization of the residual styrene monomer and the styrene (residual monomer and oligomer) and the total content of the trimerization product. As a result, the above residual monomers and oligomers are detected in amounts of 1.1 to 1.5% by weight of all specimens.

Table 8 indicates that the smaller the reduced viscosity η SP / C as the index of the molecular weight of HIPS, the better the flame retardancy. In particular, when? SP / C is 0.4 to 0.6, the balance of melt flow impact strength and flame retardancy is excellent.

TABLE 8

[Examples 40-50]

A composition obtained by mixing 7 parts by weight of BNPP with a 70/30 mixture of HIPS-1 / GPPS in Table 9 or 100 parts by weight of styrene resin containing a rubber-unmodified copolymer styrene resin was processed in the same manner as in Example 6. To prepare specimens for evaluation of MFR, Izod impact strength, non-cat softening temperature and flame retardancy. The results are shown in Table 9. According to the above measuring method, the specimen thus obtained is measured for the total content of dimerization and trimerization products of residual styrene monomer and styrene (residual monomer and oligomer). As a result, the above residual monomers and oligomers are detected in amounts of 1.1 to 1.5% by weight of all specimens.

Table 9 shows that GPPS with low molecular weight shows better falling flame retardancy than others. In particular, the use of GPPS having a weight average molecular weight of 130,000 to 220,000 provides an excellent balance of melt flowability, impact strength and flame retardancy. In addition, the styrene resin obtained by copolymerization of methacrylic acid or maleic anhydride shows excellent heat resistance. In addition, styrene resins copolymerized with α-methylstyrene or butyl acrylate are excellent in flame retardancy.

In Table 9, Example 40 is the same as Example 22, which is incorporated by reference.

TABLE 9

[Examples 51 to 60]

, Werner Pfleiderer Corp. 제조)를 통해 용해-압출한다. 상세하게, PPE/GPPS 혼합물을 압출기 이전의 스테이지에서 320℃의 온도에서 용해시킨다. 수지 성분의 나머지와 BNPP 는 압출기 다음의 스테이지에서 사이드-공급되는데, 상기 압출기에서 혼합물은 240℃의 온도, 295rpm 및 80kg/hr의 압출량으로 용해-혼련된다.HIPS-1, GPPS-1, PPE of Table 10, and BNPP are mixed in a weight ratio of 65/35 (quantity of Table 10) / 7. Then, double screw extruder (ZSK-40mm) to feed the mixture laterally

Werner Pfleiderer Corp. Dissolution-extrusion). In detail, the PPE / GPPS mixture is dissolved at a temperature of 320 ° C. in the stage before the extruder. The remainder of the resin component and BNPP are side-fed at a stage following the extruder, in which the mixture is melt-kneaded at a temperature of 240 ° C., 295 rpm and an extrusion amount of 80 kg / hr.

The pellets thus obtained were processed by an injection molding machine (IS80A type, manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., and subjected to MFR, Izod impact strength, falling impact strength and bending strength. Samples are prepared to evaluate flexural modulus, non-cat softening temperature, heat deflection temperature, and flame retardancy. The results are shown in Table 10 and FIG. According to the above measuring method, the specimen thus obtained is measured for the dimerization of the residual styrene monomer and the styrene (residual monomer and oligomer) and the total content of the trimerization product. As a result, the above residual monomers and oligomers are detected in amounts of 1.1 to 1.5% by weight of all specimens.

TABLE 10

Tables 10 and 5 show that the presence of PPE provides an improved balance between heat resistance and hardness. In particular, when PPE is incorporated into the rubber-modified styrene resin in an amount of 3 to 8 parts by weight to give a converted viscosity η SP / C of 0.3 to 0.6, the balance of melt flowability, heat resistance, hardness, impact strength and flame retardancy is remarkably Can be improved.

[Examples 61 to 65]

The rubber-modified styrene resins, GPPS-1, PPE-1 and BHPP containing HIPS-1 and HIPS-7 in the ratios of Table 11 are mixed in a weight ratio of 60/40/7/7. The mixture is then tested and evaluated in the same manner as in Example 51. The results are shown in Table 11 and FIG. According to the above measuring method, the specimen thus obtained is measured for the dimerization of the residual styrene monomer and the styrene (residual monomer and oligomer) and the total content of the trimerization product. As a result, the above residual monomers and oligomers are detected in amounts of 1.1 to 1.5% by weight of all specimens.

TABLE 11

Tables 11 and 6 show that the use of HIPS containing large and small sized rubbers provides a significant improvement in the balance of appearance (gloss), hardness and impact strength.

Examples 66 to 68

HIPS-1, GPPS, PPE-1 and BNPP in Table 12 are mixed at a weight ratio of 60/40/6/6. The mixture is then tested and evaluated in the same manner as in Example 51. The results are shown in Table 12 and FIG. According to the above measuring method, the specimen thus obtained is measured for the dimerization of the residual styrene monomer and the styrene (residual monomer and oligomer) and the total content of the trimerization product. As a result, the above residual monomers and oligomers are detected in amounts of 1.1 to 1.5% by weight of all specimens.

TABLE 12

Tables 12 and 7 show that the combination of high molecular weight and low molecular weight GPPS provides a significant improvement in the balance of melt flow, strength and impact strength.

[Examples 69 to 85 and Comparative Examples 30 to 34]

HIPS-1, GPPS-1, PPE-1, NDPP, BNPP and TNPP in Table 13 (a) and Table 13 (b) are mixed in a weight ratio of 70/30/7. The mixture is then tested and evaluated in the same manner as in Example 51. The results are shown in Table 13 (a), Table 13 (b) and FIG. According to the above measuring method, the specimen thus obtained is measured for the dimerization of the residual styrene monomer and the styrene (residual monomer and oligomer) and the total content of the trimerization product. As a result, the above residual monomers and oligomers are detected in amounts of 1.1 to 1.5% by weight of all specimens.

Tables 13 (a), 13 (b) and 8 show the BNPP content of 1 to 98% by weight when the NPDP content is 1 to 80% by weight when the total number of carbon atoms in the substituent is 12 to 25 as the number average. And when the TNPP content is 1 to 98% by weight, the balance of the flame retardancy, non-volatility, melt flowability, impact resistance, impact strength, water resistance gloss retention and surface hardness of the molded article thus obtained is excellent. In particular, as compared to the simple average of NDPP and TNPP, the mixture of these three types of monomer phosphates provides an improvement in water-resistant gloss retention and non-cat softening temperature (curves curve up in FIG. 8). Mixtures of monomeric aromatic phosphates substituted by different numbers of nonyl groups can have unique effects.

Table 13a

Table 13b

[Examples 86 to 103]

The monomeric aromatic phosphates containing NPDP, BNPP and TNPP, or HIPS-1, GPPS-1 and PPE (Table 15) at HIPS and weight ratio 10/50/40 of Table 14, and the above-mentioned Mix by weight ratio of Table 15. The mixture is then tested and evaluated in the same manner as in Example 51. The results are shown in Table 14 and Table 15. According to the above measuring method, the specimen thus obtained is measured for the dimerization of the residual styrene monomer and the styrene (residual monomer and oligomer) and the total content of the trimerization product. As a result, the above residual monomers and oligomers are detected in amounts of 1.1 to 1.5% by weight of all specimens.

Tables 14 and 15 show that when η SP / C of HIPS is between 0.4 and 0.6, the balance of melt flowability, impact strength and flame retardancy is excellent and the presence of PPE provides an improved balance between heat resistance and hardness. In particular, when PPE is incorporated into the rubber-modified styrene resin in an amount of 3 to 8 parts by weight to give a converted viscosity η SP / C of 0.3 to 0.6, the balance of melt flowability, heat resistance, hardness, impact strength and flame retardance is remarkable. Can be improved. In addition, HIPS copolymerized with α-methylstyrene or butyl acetate is excellent in flame retardancy.

TABLE 14

TABLE 15

[Examples 104 to 112]

The compositions obtained by combining HIPS-1, GPPS-1, PPE-1, polydimethylsiloxane (silicon) of Table 16, and BNPP compositions at 70/30 / (0 or 7) (amount in Table 16) were tested and carried out. Evaluation is carried out in the same manner as in Example 51. The results are shown in Table 16. According to the above measuring method, the specimen thus obtained is measured for the dimerization of the residual styrene monomer and the styrene (residual monomer and oligomer) and the total content of the trimerization product. As a result, the above residual monomers and oligomers are detected in amounts of 1.1 to 1.5% by weight of all specimens.

Table 16 allows the use of silicone to reduce the thermal shrinkage of the molded article, resulting in easier molding and drop off and improved flame retardancy. This suggests that the incorporation of silicon mitigates the orientation of the molded article.

TABLE 16

[Examples 113 to 118]

A resin composition containing a styrene resin having a formulation of Table 17 and another thermoplastic resin was prepared and evaluated in the same manner as in Example 51. The results are shown in Table 17.

TABLE 17

[Examples 119 to 124 and Comparative Example 35]

A composition obtained by combining PPE, UVA, HALS, and TiO ₂ with BNPP in a weight ratio of Table 18 to 100 parts by weight of a styrene resin containing HIPS-1 and GPPS-1 at a weight ratio of 60/40 in the same manner as in Example 51 The specimen is processed to prepare a specimen evaluated according to the above light resistance test method. For comparison, the flame retardant flame retardant polystyrene was evaluated by halogen flame retardant (BEO). The results are shown in Table 18.

Table 18 shows that the flame retardant polystyrene containing the flame retardant of the present invention exhibits excellent light resistance compared to halogen flame retardant polystyrene.

TABLE 18

[Examples 125 to 132 and Comparative Examples 36 to 43]

Rubber-modified polystyrenes having different contents of residual styrene monomers and oligomers are produced by varying the polymerization temperature and the amount of chain transfer agent to produce polystyrenes having a large content of residual styrene monomers and oligomers (dimerization and trimerization products of styrene). Next, HIPS obtained by purification of HIPS-1 and the polystyrene are prepared by compounding. 7 parts by weight of tris (nonylphenyl) phosphate (TNPP), tris (diisopropylphenyl) phosphate (TDIP), tris (phenylphenyl) phosphate (TPPP) or bis (nonylphenyl) phenylphosphate (BNPP) The composition obtained by combining the rubber-modified styrene resin with 100 parts by weight of the styrene resin obtained by mixing GPPS-1 was processed in the same manner as in Example 51 to prepare a specimen for evaluation of flame retardancy. The results are shown in Table 19 and FIG.

Tables 19 and 9 show that flame retardants with more than 50% by weight of volatile loss at 400 ° C., such as BNPP, exhibit excellent flame retardancy and therefore do not rely heavily on flame retardance for residual styrene monomer and oligomer content.

However, among flame retardants, aromatic phosphates with low volatility at 400 ° C. rely heavily on flame retardancy for residual monomers and oligomers. Therefore, if the content of the residue is 1% by weight or less, the flame retardancy of the resin composition can be greatly improved.

TABLE 19

[Examples 133 to 161 and Comparative Examples 44 to 47]

HIPS or PPE with different converted viscosity η SP / C as monomer aromatic phosphate and TNPP, TDIP or TPPP are the residual styrene monomer and the total content of dimerization and trimerization products of styrene is 0.5% by weight Into the percent composition. The composition thus obtained is then tested and evaluated in the same manner as in Example 51. The results are shown in Tables 20-22.

Tables 20 to 22 show melt flowability, impact strength and flame retardancy when the total content of dimerization and trimerization of styrene monomer in the molded part and styrene in the molded part is 1.0 wt% or less and the η SP / C of HIPS is 0.4 to 0.6. The balance is excellent. In addition, the presence of PPE improves the balance of heat resistance and hardness. In particular, when PPE having a reduced viscosity η SP / C of 0.3 to 0.6 is incorporated into the rubber-modified styrene resin in an amount of 3 to 8 parts by weight, the balance of melt flowability, heat resistance, hardness, impact strength and flame retardancy is further improved. . When the content of TNPP, TDIP and TPPP is 3 to 30 parts by weight, the property is greatly improved.

TABLE 20

TABLE 21

Table 22

[Example 162 and Comparative Examples 48 to 53]

A resin composition containing HIPS-1, GPPS, PPE-1 and BNPP is prepared at a weight ratio of 60/40/7/7.

, Werner Pfleiderer Corp. 제조)로 295rpm과 80kg/hr 의 압출량으로 용해-혼련해서 각종 수지 조성물을 제조한다.Specifically, a double screw extruder (ZSK-40mm) capable of subfeeding the mixture under the conditions of Table 23

Werner Pfleiderer Corp. Production) to melt-knead at 295 rpm and an extrusion amount of 80 kg / hr to prepare various resin compositions.

The resin composition thus obtained is then processed through an injection molding machine (resin temperature: 230 ° C.) to prepare a specimen for evaluation of flame retardancy and appearance. The results are shown in Table 23.

TABLE 23

The following facts are shown in Table 23.

If the mixture is melt-kneaded without separating the resin component from the polymer additive, innocuous polyphenylene ethers are prepared and are markedly degraded in appearance and in particular in tensile elongation.

In addition, if the polyphenylene ether content of the resin component fed in the stage before the extruder falls below 50% by weight, the shearing force cannot be applied and a costly material is produced.

[Examples 163 to 170 and Comparative Examples 54 to 57]

The following resin compositions are mechanically mixed and then melt-kneaded through a subfeedable double-screw extruder (ZSK, Werner Pfleiderer Corp .; cylinder inner diameter D = 40 mm or 70 mm) (see FIG. 10).

For the preparation of the master batches (MB-1, MB-2), the resin component is fed through the main feeder at a stage before the extruder (above the secondary feed opening), in which the melter is dissolved at a barrel temperature of 320 ° C. . Subsequently, BNPP is fed through a subfeeder at a stage following the extruder (under the subfeed opening), in which the melt is kneaded with the mixture at a barrel temperature of 270 ° C. (rotational speed: 295 rpm). ; Extrusion amount: 80 kg / hr).

MB-1: PPE-1 / BNPP = 65/35

MB-2: PPE-1 / GPPS-1 / BNPP = 40/40/20

A final composition containing HIPS-1, GPPS-1, PPE-1 and BNPP at a ratio of 60/40/7/7 is prepared by the following method (feed process I, II or III):

I (using MB-1): HIPS-1 / GPPS-l / MB-1 / BNPP

Residual components other than MB-1 and BNPP are fed through the main feeder at a stage prior to the extruder, where the extruder is dissolved at a barrel temperature of 270 ° C. Subsequently, BNPP is fed through a subfeeder at a stage following the extruder, in which the melt-kneaded with the mixture at a barrel temperature of 270 ° C. (rotational speed: 295 rpm; extrusion amount: 80 kg / hr).

II (using MB-2): HIPS-1 / GPPS-l / MB-2

All components are fed through the main feeder and then melt-kneaded at a barrel temperature of 270 ° C. (speed: 295 rpm; extrusion volume: 80 kg / hr).

III (without master batch): HIPS-1 / GPPS-1 / PPE-1 / BNPP

PPE-1 and GPPS-1 are extruded at a weight ratio of 7/5 at the stage before the extruder under the above conditions as the master batch. Subsequently, at the stage following the extruder, the residual resin component and the components other than BNPP are fed through one sub feeder and extruded under the same conditions as the composition while the BNPP is fed through another sub feeder.

The pellets thus obtained were then processed at the cylinder temperature of 230 ° C. and the mold temperature of 60 ° C. with the same injection molding machine as described in Example 51 to prepare samples for evaluation of various physical properties. The results are shown in Table 24.

TABLE 24

[Examples 171 to 176 and Comparative Examples 58 to 65]

To prepare resin compositions containing 60/40/7/7 fertilizers HIPS-1, GPPS-1, PPE-1 and BNPP, the master batches in Table 25 were each dissolved-through a subfeedable double screw extruder, respectively. The mixture is kneaded and then dissolved and kneaded in the following feeding steps (A, B and C steps).

In the first stage extrusion (preparation of the master batch), the resin component is fed through the main feeder and then dissolved at a barrel temperature of 320 ° C. Subsequently, BNPP is fed through a subfeeder and then dissolved and kneaded with the resin composition at a barrel temperature of 270 ° C. Subsequently, in the second stage extrusion, the material is melt-kneaded at a barrel temperature of 270 ° C. in feed processes A, B and C (see Table 26). Extrusion conditions of these feed processes include extrusion rates of 295 rpm and 80 kg / hr in the first and second stages.

TABLE 25

The pellets thus obtained were processed at the cylinder temperature of 230 ° C. and the mold temperature of 60 ° C. with the same injection molding machine as in Example 45 to prepare specimens for evaluating the respective physical properties. The results are shown in Table 26 and FIG.

TABLE 26

[Supply Process (Reference, Figure 11)]

Process A: Main Supply (Components other than BNPP)

Wealth Supply (BNPP)

Process B: Main Supply (Master Batch)

Wealth Supply (BNPP)

Secondary feed (master batch, ingredients other than BNPP)

Process C: Main Supply (PPE / GPPS)

Wealth Supply (BNPP)

Secondary feed (other than PPE / GPPS and BNPP)

Tables 26 and 12 show glass transition temperatures (Tg) of 70 to 100 ° C. obtained by combining polyphenylene ether, monomeric aromatic phosphate (BNPP), and any rubber-modified styrene resin or rubber-unmodified styrene resin. It is shown that when the master batch is melt-kneaded with the residual component, a flame retardant resin composition having excellent fall impact strength can be obtained. If the glass transition temperature of the master batch exceeds 100 ° C., it is shown that the obtained resin composition is highly dependent on the fall impact strength on the kneading parameters.

[Industry availability]

The incorporation of the low volatile flame retardant for the styrene resin of the present invention in the styrene resin composition causes remarkably little mold precipitation after long-lasting molding, and provides excellent flame retardancy, impact resistance, heat resistance, melt flowability, water resistance gloss retention, and surface hardness of the molded article. The resin composition shown can be provided.

Resin compositions containing low volatility flame retardants for styrene resins can be used in housings, chassis or components of homes such as VTRs, panel boards, TVs, audio players, capacitors, receptacles, radiotape players / recorders, video tape housings, video discs. Players, air conditioners, humidifiers and electric heaters; Housings, chassis or parts of OA (office automation) devices, such as CDROM mainframes (mechanical chassis), printers, facsimiles, PPCs, CRTs, word processors, copiers, electronic cash registers, office computer systems, floppy disk drives, keyboards , Typewriters, ECTs, calculators, toner cartridges and telephones; Electrical and electronic components such as connectors, coil bobbins, switches, relays, relay sockets, LEDs, various capacitors, AC adapters, FBT high pressure bobbins, FBF cases, IFT coil bobbins, jacks, volume shafts shaft) and motor parts; Automotive parts such as instrument clusters, radiator grilles, clusters, speaker grilles, louvers, console boxes, defroster garnishes, ornaments, fuse boxes, relay cases and connector shift tapes; And suitable for various other applications.

Claims (30)

Low volatility flame retardant for styrene resins consisting of aromatic phosphates represented by formula (I): [Formula I]

(Wherein a, b, and c independently represent an integer of 1 to 3; R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a halogen-free alkyl group having 1 to 30 carbon atoms and isopropyl The total number of carbon atoms in the substituents represented by R ₁ , R ₂ , and R ₃ is on average 12 to 25 per molecule of aromatic phosphate, provided that the substituents of the plurality of said aromatic phosphates, flame retardants having different substituents The total number of carbon atoms in R ₁ , R ₂ , and R ₃ is expressed as the total number average of flame retardants, which is the sum of the product of the mass portion of each said aromatic phosphate and the total number of carbon atoms of the substituents in said aromatic phosphate, respectively)) . A flame retardant as in claim 1 wherein the total number of carbon atoms in substituents R ₁ , R ₂ , and R ₃ is 14-22. A flame retardant as in claim 1 wherein the total number of carbon atoms in substituents R ₁ , R ₂ , and R ₃ is 16-20. The flame retardant according to claim 1, wherein the flame retardant consists of nonylphenyl diphenyl phosphate, bis (nonylphenyl) phenyl phosphate, and tris (nonylphenyl) phosphate. The flame retardant according to claim 4, wherein the total number of carbon atoms in substituents R ₁ , R ₂ , and R ₃ is 16-20. The flame retardant according to any one of claims 1 to 5, wherein the content of aromatic phosphates having a total number of carbon atoms of 12 or less in substituents R ₁ , R ₂ , and R ₃ is 20% by weight or less. The flame retardant according to any one of claims 1 to 5, characterized in that the flame retardant has an acid value of 1 mgKOH or less as defined in JIS-K6751 or the flame retardant has an alkylphenol content of 1 wt% or less. Flame retardant. The flame retardant according to any one of claims 1 to 5, wherein the total content of aluminum, magnesium, sodium and antimony in the flame retardant is 1,000 ppm by weight or less. 6. Flame retardant according to any one of the preceding claims, characterized in that the flame retardant also consists of phenolic antioxidants inhibited in an amount of 1 to 1,000 ppm by weight. The flame retardant according to any one of claims 1 to 5, wherein the flame retardant is a dropwise flame retardant. A resin composition comprising 100 parts by weight of a styrene resin and 1 to 50 parts by weight of the flame retardant according to claims 1 to 10. The resin composition according to claim 11, wherein the resin composition is composed of 100 parts by weight of styrene resin and 1 to 20 parts by weight of the flame retardant. The resin composition according to claim 12, wherein the resin composition is composed of 100 parts by weight of styrene resin and 3 to 8 parts by weight of the flame retardant. The method of claim 11, wherein the resin composition is further selected from polyphenylene ether, aromatic polycarbonate or polyphenylene ether and aromatic polycarbonate in an amount of 1 to 500 parts by weight per 100 parts by weight of the styrene resin. Resin composition comprising both. The resin composition according to any one of claims 11 to 13, wherein the resin composition is also made of polyphenylene ether in an amount of 1 to 40 parts by weight per 100 parts by weight of the styrene resin. The resin composition according to claim 15, wherein the amount of the polyphenylene ether is in an amount of 3 to 8 parts by weight per 100 parts by weight of the styrene resin. The resin composition according to any one of claims 11, 12, 13 or 16, wherein the resin composition is also made of polyorganosiloxane in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the styrene resin. 18. The resin composition according to claim 17, wherein the polyorganosiloxane is polydimethylsiloxane. The resin composition according to any one of claims 11, 12, 13, 16 or 18, wherein the converted viscosity η Sp / C of the styrene resin is 0.4 to 0.6 dl / g. The resin composition according to claim 14, wherein the resin composition is made of a polyphenylene ether having a viscosity η Sp / C of 0.3 to 0.6 dl / g. 19. The method of claim 11, 12, 13, 16 or 18, wherein the styrene resin has a small size particle rubber having a weight-average particle diameter of 0.1 to 0.9 mu m and a weight-average particle diameter of 1.0 to 3.0 mu m. And a rubber-modified styrene resin composed of a large size particle rubber having. Flame retardant of a resin composition consisting of 100 parts by weight of a styrene resin and 3 to 30 parts by weight of a flame retardant selected from the group consisting of: flame retardant (1) consisting of an aromatic phosphate represented by the following general formula (I): [Formula I]

(Wherein a, b, and c independently represent an integer of 1 to 3; at least one R ₁ , R ₂ , and R ₃ represent an isopropyl group or an aryl group, and other R ₁ , R ₂ , and R ₃ each independently represents a halogen-free alkyl group having 1 to 30 carbon atoms that is not a hydrogen atom or an isopropyl group, and the total number of carbon atoms in the substituents represented by R ₁ , R ₂ , and R ₃ is 1 molecule of the aromatic phosphate Wherein the flame retardant has a plurality of aromatic phosphates having different substituents, the substituents R ₁ , R ₂ , and R ₃ of the flame retardant represented by the total number average of the flame retardant, Sum of the product of the mass portion of each aromatic phosphate and the total number of carbon atoms of the substituents in each aromatic phosphate), and (2) tris (nonylphenyl) phosphate (wherein the amount of aromatic vinyl And the total amount of dimerization and Sanhe solution heat remaining in the resin composition is not more than 1% by weight). The flame retardant resin composition of claim 22 wherein the resin composition is further comprised of polyphenylene ether in an amount of 1 to 10 parts by weight per 100 parts by weight of the styrene resin. The flame retardant resin composition according to claim 23, wherein the styrene resin has a converted viscosity η Sp / C of 0.4 to 0.6 and the polyphenylene ether has a converted viscosity η Sp / C of 0.3 to 0.6. The flame retardant resin composition according to any one of claims 22 to 24, wherein the aryl group represented by R ₁ , R ₂ , and R ₃ is selected from the group consisting of phenyl group, benzyl group and cumyl group. The flame retardant resin composition according to any one of claims 22, 23, and 24, wherein the flame retardant resin composition is a dropwise flame retardant resin composition. 27. A method of preparing a resin composition according to any one of claims 14-21 and 23-26, comprising the steps of: dividing a styrene resin into two batches; Preparing a first resin composition composed of one of the two batches of polyphenylene ether in an amount of at least 50% by weight based on the amount of the styrene resin and the first resin composition; Dissolving the first resin composition at a temperature of 250 ° C. to 350 ° C. in the previous stage of the twin-screw extruder; And a second resin comprising the first resin composition at the temperature of 200 ° C. to 300 ° C. of the twin-screw extruder at a later stage, the styrene resin and the other two batches of the flame retardant according to claims 23 to 25. Dissolution-extrusion with the composition. 29. The twin-screw extruder of claim 27, wherein the twin-screw extruder has an L / D ratio of 20-50 (D represents the inner diameter of the cylinder and L represents the length of the screw), each different from the end of the twin-screw extruder. A plurality of feed openings comprising a main feed opening and a sub feed opening spaced apart, wherein a kneading zone is provided between the plurality of supply openings and at the end of the twin-screw extruder and at the end of the twin-screw extruder Wherein the kneading zones each have a length of 3D to 10D. 27. A method of preparing a resin composition according to any one of claims 14 to 21 and 23 to 26, comprising the following steps: any one of claims 1 to 10 or any of claims 23 to 25. Preparing a master batch consisting of a resin composition consisting of a polyphenylene ether and a flame retardant used according to one of the preceding claims, or both the resin composition and the styrene resin, a rubber-modified styrene resin or a styrene resin and a rubber-modified styrene resin Preparing a master batch consisting of: adding residues of the components of the resin composition according to any one of claims 14 to 21 and 23 to 26 to the master batch to produce a mixture; and Dissolving-kneading the mixture, wherein the master batch has a glass transition temperature of 70 ° C to 100 ° C. The method of claim 1 having a temperature rise rate of 40 ° C./min, and upon heating test in nitrogen, a weight loss of 0 to 10% by weight at a temperature of 300 ° C. and 50 to 100% by weight at a temperature of 400 ° C. Low volatility aromatic phosphate flame retardant.

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